Single-material objects, in particular recyclable objects, and recycling thereof

Abstract

The present invention relates to a single-material object, in particular a recyclable object, consisting predominantly of long-chain polyamide comprising at least two elements: - at least one first element consisting of at least one extruded or blow-extruded part intended for transporting, dispensing and / or storing a fluid, comprising at least one layer that consists of a first composition comprising at least 30% by weight, relative to the total weight of the first element, of at least one homopolyamide or at least one copolyamide having a C / N ratio higher than or equal to 8; - at least one second element consisting of at least one injected part that consists of a second composition comprising at least 30% by weight, relative to the total weight of the second element, of at least one homopolyamide or at least one copolyamide as defined above for the first composition, and wherein the first and second elements are able to at least partially adhere to one another.

Description

[0001] DESCRIPTION

[0002] TITLE: MONOMATERIAL OBJECTS, PARTICULARLY RECYCLABLE, AND THEIR RECYCLING

[0003] [Technical field]

[0004] The present invention relates to single-material objects, in particular recyclable objects, comprising at least two elements, their manufacturing process as well as their recycling process and the compositions thus obtained as well as their use for the manufacture of objects, in particular single-material objects.

[0005] The circular economy helps limit waste production, the depletion of the planet's resources, and environmental impact. Currently, we are particularly looking to produce objects using materials that, after recycling, will have sufficient properties to allow their use for high-performance applications and not only for lower-performance applications such as street furniture or roads. In order to facilitate the recycling of parts used for 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 made mostly of polyamide, tubes made mostly of polyamide, etc.).

[0006] Patent EP 3 081 109 B1 proposes, in order to facilitate their recycling, a sports shoe whose upper part and sole are mainly or even entirely made of the same thermoplastic base material.

[0007] Patent application WO 2020 / 201370 A1 proposes a method for recycling sports shoes in which the shoe is crushed and then melted. This document, like the previous one, focuses on thermoplastic polyurethanes (TPUs).

[0008] Application US 2017 / 0151470 A1 relates to a ball, in particular a soccer ball, a method of manufacturing and recycling the ball. The ball consists of a bladder, an intermediate layer and an outer layer, the bladder and the two layers being made of a majority component by weight of a material of a first class of material selected from polyurethane, polyvinyl chloride, polyethylene, polyamide and polypropylene.

[0009] International application WO 2021 / 148148 A1 relates to a lined article of clothing comprising an outer layer, an inner layer and a lining between the two layers. Each layer contains a majority of a material of the same family selected from thermoplastic polymers, in particular a recycled polyester or a virgin polymer selected from thermoplastic polyurethanes (TPU), polyamides (PA), polyethylene terephthalate (PET) or polybutylene terephthalate (PBT). Polyesters have the disadvantage of being very sensitive to hydrolysis.

[0010] All of these patent applications described above only deal with the sports shoe, sports ball or article of clothing but not with parts enabling the transport, distribution and / or storage of fluid in different means of transport.

[0011] The invention therefore aims to propose a single-material object, in particular recyclable, so as to enable the obtaining of a composition for recycling that can be used for applications for the manufacture of objects, in particular single-material objects, or for the manufacture of a system for transporting, distributing and / or storing a fluid.

[0012] In particular, in the case of systems for transporting, distributing and / or storing a fluid, in particular for a device with a thermal or electric engine such as an airplane, a drone, an aircraft, a truck or an automobile, it is generally tedious and / or expensive to separate the various elements constituting said system (in particular pipes, tanks and connectors or other injected parts) with a view to sorting them and possibly recycling them. These separation and sorting steps, which must be carried out manually by an operator, do not currently allow the recycling of these materials to be processed quantitatively, and therefore in an economically viable manner.

[0013] The need to separate and sort these different elements is therefore a significant obstacle to their recycling today.

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

[0015] Thus, the present invention relates to a single-material object, in particular recyclable, consisting mainly of long-chain polyamide comprising at least two elements:

[0016] - at least one first element consisting of at least one extruded or blown extruded part intended for the transport, distribution and / or storage of a fluid, in particular chosen from a tube and a reservoir, comprising at least one layer consisting of a first composition comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the first element, of at least one homopolyamide or at least one copolyamide, said at least one homopolyamide or at least one copolyamide of the first composition having a C / N ratio greater than or equal to 8, in particular greater than or equal to 9, particularly greater than or equal to 10, said at least one homopolyamide and said at least one copolyamide representing, independently of one another, a repeating unit chosen from a unit obtained from the polycondensation of at least one C4-C36 amino acid,a unit obtained from the polycondensation of at least one C4-C lactam, 36 and an XY unit obtained from the polycondensation of: at least one diamine, said diamine being chosen from a linear or branched aliphatic diamine, a cycloaliphatic diamine and a semi-arylaliphatic diamine or a mixture thereof, and at least one dicarboxylic acid, said diacid being chosen from: an aliphatic diacid, a cycloaliphatic diacid and an aromatic diacid or a mixture thereof, said diamine and said diacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms,

[0017] - at least one second element consisting of at least one injected part, in particular chosen from a connector, consisting of a second composition comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the second element, of at least one homopolyamide or at least one copolyamide as defined above for the first composition, and said first and second elements being able to adhere at least partially to each other. By "mono-material object" is meant an object consisting mainly of the same material, in this case a long-chain polyamide.

[0018] More precisely, by "single-material object", it is necessary to understand an object comprising at least two elements, with each element being made up of compositions respectively comprising at least one polymer matrix, with said polymer matrix comprising predominantly, that is to say more than 50% by weight, relative to its total weight, at least one long-chain polyamide as defined according to the invention.

[0019] For the purposes of the invention, the single-material object may in particular be an object comprising at least two elements, with each element being single-material, i.e. each element being made up mainly of the same material as defined according to the invention.

[0020] By "polymeric matrix" is meant the part of the composition consisting exclusively of polymers, i.e. non-polymeric fillers and additives are excluded here.

[0021] Preferably, said polymeric 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.

[0022] According to one embodiment, a “mono-material object” within the meaning of the invention is an object comprising at least two elements, with at least one element, preferably each element, being made up of compositions comprising predominantly, i.e. more than 50% by weight, relative to their total weight, at least one long-chain polyamide as defined according to the invention.

[0023] Preferably at least one element, preferably each element, consists of compositions 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 long-chain polyamide as defined according to the invention.

[0024] According to one embodiment, a mono-material object of the invention is an object comprising at least two elements, with at least one element, preferably each element, consisting of compositions 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, relative to their total weight, of short-chain polyamides, that is to say 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] According to one embodiment, a mono-material object of the invention comprises 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, relative to its total weight, of short-chain polyamides, that is to say 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.

[0026] The expression "mono-material object, in particular recyclable, consisting mainly of long-chain polyamide" means, for example, that said object is made up of a single family of material and which comprises at least 50% by weight of long-chain polyamide having a C / N ratio, that is to say having an average number of carbon atoms per nitrogen atom, greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10. According to one embodiment, the first element of said mono-material object of the invention may consist of at least one extruded or blown extruded part intended for the transport, distribution and / or storage of a fluid which is chosen from a tube and a reservoir. Said tube or reservoir may contain from one to five layers.

[0027] In one embodiment, said tube or reservoir comprises only polyamide layers. According to one embodiment, the first element of said mono-material object of the invention comprises at least 60%, in particular at least 70%, in particular 80%, advantageously 90%, more advantageously 100% by weight of long-chain polyamide.

[0028] When said first element of said mono-material object of the invention comprises less than 100% by weight of long-chain polyamide, the balance to 100% is made with another polyamide which may or may not be long-chain or with another polymer such as EVOH (ethylene vinyl alcohol)

[0029] Advantageously, said single-material object of the invention comprises at least 60%, in particular at least 70%, in particular 80%, advantageously 90%, more advantageously 100% by weight of long-chain polyamide.

[0030] When said object comprises less than 100% by weight of long-chain polyamide, the balance to 100% is made with another polyamide which may or may not be long-chain or with another polymer such as EVOH (ethylene vinyl alcohol).

[0031] In one embodiment, a copolyamide with amide units (Bal) and polyether units (Ba2) is excluded from said first composition.

[0032] In another embodiment, a copolyamide with amide units (Bal) and polyether units (Ba2) is excluded from said second composition.

[0033] In yet another embodiment, a copolyamide with amide units (Ba1) and polyether units (Ba2) is excluded from said first composition and said second composition. Advantageously, said single-material object defined above is chosen from an automobile, truck, aircraft and drone part.

[0034] The term "fluid" means air, oil (for example for cooling the automatic gearbox "TOC" (Transmission Oil Cooler), water, a urea solution, a refrigerant, in particular R1234yf, a glycol-based coolant, a fuel such as gasoline, in particular bio-gasoline or diesel, in particular bio-diesel, hydrogen or a coolant, in particular a battery or fuel cell. In one embodiment, said fluid is a coolant, in particular a battery or fuel cell.

[0035] In another embodiment, said fluid is hydrogen.

[0036] According to one embodiment, the second element of said single-material object of the invention may consist of at least one injected part intended for the transport, distribution and / or storage of a fluid which is chosen from a connector.

[0037] According to one embodiment, the single-material object of the invention may be a system for transporting, distributing and / or storing a fluid, in particular for a device with a thermal or electric engine such as an airplane, a drone, an aircraft, a truck or an automobile.

[0038] It may in particular be a system combining at least one pipe and at least one connector, preferably a system combining at least one pipe and two connectors, with said connector allowing the assembly of said pipes.

[0039] It may also be a system combining at least one tank and at least one connector, preferably a system combining at least one tank, at least one connector, and at least one pipe, with said connector allowing the assembly of said pipe and said tank.

[0040] According to one embodiment, the single-material object of the invention may be a system for transporting, distributing and / or storing a fluid, in particular for a device with a thermal or electric engine such as an airplane, a drone, an aircraft, a truck or an automobile, combining at least one first element consisting of at least one extruded or blown extruded part as defined according to the invention and at least one second element consisting of at least one injected part as defined according to the invention, preferably at least two second elements consisting of at least one injected part as defined according to the invention.

[0041] In particular, the single-material object of the invention may be a system for transporting, distributing and / or storing a fluid, in particular for a device with a thermal or electric engine such as an airplane, a drone, an aircraft, a truck or an automobile, combining at least a number N of first elements consisting of at least one extruded or blown extruded part as defined according to the invention and at least a number N+1 of second elements consisting of at least one injected part as defined according to the invention, with N being an integer greater than or equal to 1, in particular greater than or equal to 2, for example between 1 and 100.

[0042] With regard to the long-chain homopolyamide and copolyamide of the compositions of the first and second elements.

[0043] The nomenclature used to define polyamides is described in ISO 1874-1:2011 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", particularly on page 3 (tables 1 and 2) and is well known to those skilled in the art.

[0044] Said long-chain homopolyamide and copolyamide (also more simply called “long-chain polyamide” within the meaning of the invention) is a polyamide having a C / N ratio, that is to say having an average number of carbon atoms per nitrogen atom, greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10.

[0045] In a first variant of the invention, the repeating unit is a unit obtained from the polycondensation of at least one C4-C36 amino acid (or aminocarboxylic acid). Advantageously, said aminocarboxylic acid comprises from 9 to 12 carbon atoms. It can thus be chosen from 9-aminononanoic acid (noted 9), 10-aminodecanoic acid (noted 10), 11-aminoundecanoic acid (noted 11) and 12-aminododecanoic acid (noted 12), advantageously the aminocarboxylic acid is 11-aminoundecanoic acid.

[0046] In a second variant of the invention, the repeating unit is a unit obtained from the polycondensation of at least one C4-C36 lactam. Advantageously, the lactam comprises from 9 to 12 carbon atoms. It can thus be chosen from decanolactam (denoted 10), undecanolactam (denoted 11) and laurolactam or lauryllactam (denoted 12), advantageously the lactam is lauryllactam.

[0047] However, it is entirely possible to envisage using a mixture of two or more aminocarboxylic acids, a mixture of two or more lactams, but also a mixture of one, two or more aminocarboxylic acids with one, two or more lactams.

[0048] More particularly preferably, the repeating unit is obtained from a single aminocarboxylic acid or a single lactam.

[0049] XY repeating pattern

[0050] In another variation, the repeating pattern is an XY pattern.

[0051] The repeating unit XY is a unit which can be obtained from the polycondensation of at least one diamine, said diamine being chosen from a linear or branched aliphatic diamine, a cycloaliphatic diamine and a semi-arylaliphatic diamine or a mixture thereof, and at least one dicarboxylic acid, said diacid being chosen from: an aliphatic diacid, a cycloaliphatic diacid and an aromatic diacid or a mixture thereof,

[0052] The molar proportions of diamine and dicarboxylic acid are preferably stoichiometric.

[0053] Said diamine comprises from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms.

[0054] In one embodiment, said diamine comprises from 6 to 12 carbon atoms.

[0055] In the case where the diamine used to obtain this repeating unit XY is an aliphatic diamine which has a linear main chain, this linear main chain may, where appropriate, comprise one or more methyl and / or ethyl substituent(s); in this latter configuration, we speak of a "branched aliphatic diamine". In the case where the main chain does not comprise any substituent, the aliphatic diamine is called a "linear aliphatic diamine". Whether or not it comprises methyl and / or ethyl substituents on the main chain, the aliphatic diamine used to obtain this repeating unit XY comprises from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, in particular from 9 to 18 carbon atoms.

[0056] When this diamine is a linear aliphatic diamine, it then corresponds to the formula H2N- (CH2)x-NH2 and can be chosen for example from butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, hexadecanediamine, octadecanediamine and octadecenediamine. The linear aliphatic diamines which have just been cited can all be bio-resourced within the meaning of standard ASTM D6866.

[0057] When this diamine is a branched aliphatic diamine, it may in particular be 2-methylpentanediamine, 2-methyl-1,8-octanediamine or trimethylene (2,2,4 or 2,4,4) hexanediamine.

[0058] The cycloaliphatic diamine may be chosen, for example, from 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-4,4'-diamino-dicyclohexylmethane commonly referred to as "BMACM" or "MACM" (and denoted B hereinafter), p-bis(aminocyclohexyl)methane commonly referred to as "PACM" (and denoted P hereinafter), isopropylidenedi(cyclohexylamine) commonly referred to as "PACP", isophorone-diamine (denoted IPD hereinafter) and 2,6-bis(amino methyl)norbornane commonly referred to as "BAMN" or bis(aminomethyl)cyclohexane commonly referred to as "BAC".

[0059] A non-exhaustive list of these cycloaliphatic diamines is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405).

[0060] When this diamine is a semi-arylaliphatic diamine, it is for example chosen from 1,3-xylylene diamine and 1,4-xylylene diamine.

[0061] The dicarboxylic acid comprises from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, in particular from 6 to 12 carbon atoms.

[0062] When the dicarboxylic acid is aliphatic, it can be chosen from aliphatic, linear or branched dicarboxylic acids

[0063] When the dicarboxylic acid is aliphatic and linear, it can 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), brassylic 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.

[0064] The fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in document EP 0471566. When the dicarboxylic acid is aromatic, it can be chosen from terephthalic acid (denoted T), isophthalic acid (denoted I) and a naphthalenic acid (denoted N).

[0065] In one embodiment, the composition of the first element and that of the second element are each made of a single homopolyamide.

[0066] In another embodiment, the homopolyamide of the composition of the first element and that of the second element is an aliphatic semi-crystalline homopolyamide.

[0067] A semi-crystalline homopolyamide, within the meaning of the invention, designates a material which is generally solid at room temperature, and which softens upon an increase in temperature, in particular after passing its glass transition temperature (Tg), and which can exhibit a clear melting upon passing its so-called melting temperature (Tf), and which becomes solid again upon a decrease in temperature below its crystallization temperature.

[0068] The semi-crystalline homopolyamide, within the meaning of the invention, has a melting temperature (Tf) measured according to the ISO 11357-3:2013 standard by DSC, and a crystallization enthalpy measured during the cooling step at a rate of 20K / min by DSC according to the ISO 11357-3:2013 standard greater than 25 J / g, preferably greater than 40 J / g.

[0069] Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2:2013 and 11357-3:2013 respectively.

[0070] The number-average molecular mass Mn of said semi-crystalline homopolyamide is preferably in a range from 10,000 to 85,000, in particular from 10,000 to 60,000, preferably from 10,000 to 50,000, even more preferably from 12,000 to 50,000. In a first variant, the first and second compositions of the two elements are different.

[0071] By different, it is meant that the homopolyamide or copolyamide of the first composition is different from that of the second composition, or the homopolyamide or copolyamide are identical but in this case, the compositions differ by a constituent other than the polyamide.

[0072] Advantageously, in the latter case, only one of the two compositions comprises a filler, the other being devoid of it.

[0073] The term filler includes glass beads, fibers such as glass and carbon fibers, talc, carbon black, and carbon nanotubes.

[0074] Preferably, the injected part comprises glass or carbon fibers or glass beads.

[0075] In one embodiment, the injected part comprises a current-conducting filler, such as carbon black or carbon nanotubes (CNTs). In another embodiment, the extruded part and the injected part comprise a current-conducting filler, such as carbon black or carbon nanotubes (CNTs).

[0076] In a second variant, the first composition and the second composition comprise the same polyamide.

[0077] Advantageously, the first composition and the second composition comprise the same polyamide, in particular a PAH, PA12, PA1010, PA1012, PA610 and PA612.

[0078] In a third variant, the single-material object is made mainly of long-chain aliphatic polyamide or a mixture of elements made of long-chain aliphatic and semi-aromatic polyamide.

[0079] In a fourth variant at least 10% by weight of the units, in particular at least 30% by weight, constituting said at least one homopolyamide or said at least one copolyamide of the first composition and the second composition are identical.

[0080] In one embodiment of these four variants, said long-chain homopolyamide is chosen from: polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1212), polyamide 612 (PA612), polyamide 610 (PA610) or a mixture thereof or a copolyamide thereof, in particular PA11, PA12, PA610 and PA612.

[0081] Regarding copolyamide with amide units (Bal) and polyether units (Ba2) (PEBA)

[0082] The definition below is valid both for the PEBA optionally excluded from the compositions of the first and second elements and for the PEBA possibly present in the compositions of the first, second and third elements, as defined below. Polyether block amide (PEBA) are copolymers with amide units (Ba1) and polyether units (Ba2), said amide unit (Ba1) corresponding to an aliphatic repeating unit chosen from a unit obtained from at least one amino acid or a unit obtained from at least one lactam, or an XY unit obtained from polycondensation:

[0083] - at least one diamine, said diamine being preferably chosen from a linear or branched aliphatic diamine or a mixture thereof, and

[0084] - at least one dicarboxylic acid, said diacid being preferably chosen from: a linear or branched aliphatic diacid, or a mixture thereof, said diamine and said diacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms; said polyether units (Ba2) being in particular derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol, PEBAs result in particular from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as, among others:

[0085] 1) Polyamide sequences with diamine chain ends with polyoxyalkylene sequences with dicarboxylic chain ends.

[0086] 2) Polyamide sequences with dicarboxylic chain ends with polyoxyalkylene sequences with diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic alpha-omega dihydroxylated polyoxyalkylene sequences called polyalkylene ether diols (polyetherdiols).

[0087] 3) Polyamide sequences with dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides. The copolymers of the invention are advantageously of this type.

[0088] Polyamide sequences with dicarboxylic chain ends originate, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.

[0089] Polyamide blocks with diamine chain ends are obtained, for example, by the condensation of polyamide precursors in the presence of a chain-limiting diamine. Polyamide block and polyether block polymers can also comprise randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and the polyamide block precursors.

[0090] For example, polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted. The result is a polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reactants having reacted randomly which are distributed randomly (statistically) along the polymer chain.

[0091] Polyetherdiamine, polyamide precursors and a chain-limiting diacid can also be reacted. The result is a polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reactants having reacted randomly which are distributed randomly (statistically) along the polymer chain.

[0092] Amid motif (Bal):

[0093] The amide unit (Bal) corresponds to an aliphatic repeating unit as defined above. Advantageously, the amide unit (Bal) is chosen 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, in particular polyamide 11.

[0094] More advantageously, the amide unit (Bal) is chosen from polyamide 11 and polyamide 12, in particular polyamide 11. Polyether unit (Ba2):

[0095] The polyether units are in particular derived from at least one polyalkylene ether polyol, in other words, the polyether units are made up of at least one polyalkylene ether polyol. In this embodiment, the expression "at least one polyalkylene ether polyol" means that the polyether units are exclusively made up of alcohol chain ends and therefore cannot be a polyetherdiamine triblock type compound.

[0096] The composition of the invention is therefore free of polyetherdiamine triblock.

[0097] Advantageously, the polyether units (Ba2) are chosen from polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene glycol (PO3G), polytetramethylene glycol (PTMG) and their mixtures or their copolymers, in particular PTMG.

[0098] The number-average molecular mass (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.

[0099] PEBA can be prepared by the following process:

[0100] - in a first step, the polyamide blocks (Bal) are prepared by polycondensation of the lactam(s), or of the amino acid(s), or of the diamine(s) and of the dicarboxylic acid(s); and where appropriate, of the comonomer(s) chosen from lactams and alpha-omega aminocarboxylic acids; in the presence of a chain limiter chosen from dicarboxylic acids; then

[0101] - in a second step, the polyamide blocks (Bal) obtained are reacted with polyether blocks (Ba2), in the presence of a catalyst.

[0102] The general method of two-step preparation of the copolymers of the invention is known and is described, for example, in French patent FR 2 846 332 and in European patent EP 1 482011.

[0103] The block formation reaction (Bal) usually takes place between 180 and 300°C, preferably between 200 and 290°C, the pressure in the reactor is established between 5 and 30 bars, and it is maintained for about 2 to 3 hours. The pressure is slowly reduced by bringing the reactor to atmospheric pressure, then the excess water is distilled for example for an hour or two.

[0104] Once the polyamide with carboxylic acid ends has been prepared, the polyether and a catalyst are then added. The polyether can be added in one or more steps, as can the catalyst. According to an advantageous form, the polyether is added first, the reaction of the OH ends of the polyether and the COOH ends of the polyamide begins with the formation of ester bonds and the elimination of water. As much water as possible is removed from the reaction medium by distillation, then the catalyst is introduced to complete the bonding of the polyamide blocks and the polyether blocks. This second step is carried out with stirring, preferably under a vacuum of at least 15 mm Hg (2000 Pa) at a temperature such that the reactants and the copolymers obtained are in the molten state. For example, this temperature can be between 100 and 400°C and most often 200 and 300°C.The reaction is monitored by measuring the torque exerted by the molten polymer on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the target torque or power value.

[0105] During the synthesis, one or more molecules used as antioxidants, for example Irganox® 1010 or Irganox® 245, may also be added at the most opportune moment. The PEBA preparation process can also be considered such that all the monomers are added at the beginning, in a single step, to carry out the polycondensation: of the lactam(s), or of the amino acid(s), or of the diamine(s) and of the dicarboxylic acid(s); and, where appropriate, of the other polyamide comonomer(s);

[0106] - in the presence of a chain limiter chosen from dicarboxylic acids;

[0107] - in the presence of blocks (Ba2) (polyether);

[0108] - in the presence of a catalyst for the reaction between the flexible blocks (Ba2) and the blocks (Bal). Advantageously, said dicarboxylic acid is used as a chain limiter, which is introduced in excess relative to the stoichiometry of the diamine(s).

[0109] Advantageously, the catalyst used is a derivative of a metal chosen from the group formed by titanium, zirconium and hafnium or a strong acid such as phosphoric acid, hypophosphorous acid or boric acid.

[0110] Polycondensation can be carried out at a temperature of 240 to 280°C.

[0111] Generally speaking, known copolymers with ether and amide units consist of linear and semi-crystalline aliphatic polyamide sequences (for example, Arkema's "Pebax").

[0112] In one embodiment, the copolyamide with amide units (Bal) and polyether units (Ba2) has a density greater than or equal to 1, in particular greater than or equal to 1.01, in particular greater than or equal to 1.02, as determined according to ISO 1183-3: 1999.

[0113] In one embodiment, polyetheramines are excluded from the polyether units (Ba2).

[0114] Regarding the single-material object

[0115] It consists of at least two elements: said at least one first element defined here as (El) and said at least one second element defined here as (E2).

[0116] In a first variant, it is made up of the two said elements: E1 / E2. The element El can adhere to the element E2 at least partially, in particular El and E2 adhere at least partially, in particular El and E2 adhere completely, in particular by means of an adhesive.

[0117] In a second variant, it consists of more than two elements: El / (El)n / E2 / (E2)m, n and m being from 0 to 50, in particular from 3 to 50 elements, in particular from 5 to 30 elements, in particular from 10 to 30 elements and when n=0, then m is greater than 0 and when m=0, then n is greater than 0.

[0118] It is quite obvious that when two El elements or two E2 elements are side by side, they can adhere at least partially to each other.

[0119] According to one embodiment, E1 and / or E2, preferably E1 and E2, may be intended for the transport, distribution and / or storage of a fluid, in particular for a device with a thermal or electric motor such as an airplane, a drone, an aircraft, a truck or an automobile. E1 may in particular be chosen from a pipe and a tank.

[0120] E2 can be a connector in particular.

[0121] The invention aims to protect a system combining at least one pipe or tank and at least one connector

[0122] According to one embodiment, the single-material object of the 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, with said connector allowing the assembly of said pipes.

[0123] According to one embodiment, the single-material object of the 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, with said connectors allowing the assembly of said pipes.

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

[0125] Also covered by the invention is a system combining at least 2 pipes, preferably at least 3 pipes, at least 3 connectors, preferably at least 4 connectors, and optionally at least one tank.

[0126] In one embodiment, the homopolyamides or copolyamides of elements E1 and E2 comprise an identical monomer, in particular at least 10% by weight of an identical monomer relative to the sum of the constituents of said homopolyamide or copolyamide, advantageously at least 30%. In another embodiment, said mono-material object as defined above is characterized in that at least 10% by weight of the units, in particular at least 30% by weight, constituting said at least one homopolyamide or said at least one copolyamide of the first composition and the second composition are identical, in particular said units are PAU, PA12, PA1010, PA1012, PA610 and 612 units.

[0127] In yet another embodiment, said single-material object as defined above is characterized in that the difference in C / N between 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 is less than or equal to 3, in particular less than or equal to 2, in particular less than or equal to 1.

[0128] In another embodiment, said mono-material object as defined above is characterized in that said at least one homopolyamide or said at least one copolyamide of the first composition and said at least one homopolyamide or said at least one copolyamide of the second composition comprise a monomer having an identical C / N.

[0129] The term monomer means an elementary building block such as a lactam, an amino acid or the association of a diamine with a dicarboxylic acid as defined above.

[0130] In one embodiment, said monomer is identical in each composition.

[0131] In a third variant, said single-material object may be made up of more than two elements, i.e. at least three elements: said at least one first element defined here as (El) and said at least one second element defined here as (E2) and said third element defined here as E3.

[0132] Said single-material object comprising at least one 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 with amide units (Ba1) and polyether units (Ba2) or a mixture thereof.

[0133] The third element may be an extruded or blown extruded part or an injection-molded part. In one embodiment, it consists of three elements: E1 / E2 / E3 or E1 / E3 / E2 or E3 / E1 / E2.

[0134] The element El can adhere to the element E2 at least partially, in particular El and E2 adhere at least partially, in particular El and E2 adhere completely, in particular by means of an adhesive.

[0135] Element E2 may adhere to element E3 at least partially, in particular E2 and E3 adhere at least partially, in particular E2 and E3 adhere completely, in particular by means of an adhesive. Element E1 may adhere to element E3 at least partially, in particular E1 and E3 adhere at least partially, in particular E1 and E3 adhere completely, in particular by means of an adhesive.

[0136] It would not be outside the scope of the invention if at least one other element E1 and / or E2 and / or E3 were present in said single-material object.

[0137] In a fourth variant, said single-material object may consist of more than three elements, i.e. at least four elements: said at least one first element defined here as (El), said at least one second element defined here as (E2), said third element defined here as E3 and said fourth element defined here as E4.

[0138] The third element can be an extruded or blown extruded part or an injection molded part.

[0139] The fourth element may be an extruded or blown extruded part or an injection-molded part. In one embodiment, it consists of four elements: E1 / E2 / E3 / E4 and all possible combinations of arrangement of these four elements.

[0140] Each element may adhere to the element that succeeds it at least partially, in particular each element adheres at least partially, in particular each element adheres completely. Each element may be of non-recycled origin or at least partially recycled

[0141] The expression "at least partially recycled" means that there is at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% of recycled composition in said element, said recycled composition itself comprising at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% of long chain homopolyamide or copolyamide.

[0142] In one embodiment, when the mono-material consists of three or more elements, said composition of the third element comprises at least one homopolyamide or at least one long-chain copolyamide.

[0143] In another embodiment, when the mono-material consists of three or more elements, said composition of the third element (E3) comprises at least one copolyamide with amide units (Bal) and polyether units (Ba2).

[0144] In yet another embodiment, when the mono-material consists of three or more elements, said composition of the third element comprises a mixture of at least one homopolyamide or at least one long-chain copolyamide and at least one copolyamide with amide units (Ba1) and polyether units (Ba2).

[0145] In another embodiment, the composition of the first element (El) comprises a single homopolyamide or at least one long-chain copolyamide.

[0146] In another embodiment, the composition of the second element (E2) comprises a single homopolyamide or at least one long-chain copolyamide. In another embodiment, the composition of the third element (E3) if present comprises a single homopolyamide or at least one long-chain copolyamide.

[0147] In another embodiment, the composition of the third element (E3) if present comprises a single copolyamide with amide units (Bal) and polyether units (Ba2).

[0148] In another embodiment, the composition of the first element (El) comprises a single homopolyamide or at least one long-chain copolyamide and the composition of the second element (E2) comprises a single homopolyamide or at least one long-chain copolyamide. In another embodiment, the composition of the first element (El) comprises a single homopolyamide or at least one long-chain copolyamide and the composition of the second element (E2) comprises a single homopolyamide or at least one long-chain copolyamide and the composition of the third element (E3) if present comprises a single homopolyamide or at least one long-chain copolyamide.

[0149] In another embodiment, the composition of the first element (El) comprises a single homopolyamide or at least one long-chain copolyamide and the composition of the second element (E2) comprises a single homopolyamide or at least one long-chain copolyamide and the composition of the third element (E3) if present comprises a single copolyamide with amide units (Ba1) and polyether units (Ba2).

[0150] As indicated above, the first element and the second element may adhere at least partially to each other. When they adhere at least partially to each other, the first and second elements adhere to each other by welding, insertion on a fir tree tail, clipping, or bonding using a non-polyamide adhesive in a content of 0.01% to 10% by weight, in particular 0.1% to 4% by weight relative to the total mass of the object or are introduced into each other.

[0151] Said adhesive may be a polyurethane, acrylic, acrylonitrile, polyester, polysisoprene, polybutadiene, vinyl adhesive, preferably it is chosen from a polyurethane, acrylic and polyester adhesive, advantageously it corresponds to a polyurethane adhesive.

[0152] According to another aspect, the present invention relates to a method of manufacturing a single-material object as defined above, comprising the steps of:

[0153] Providing a first element consisting of a first composition comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the first element of at least one homopolyamide or at least one long-chain copolyamide, as defined above,

[0154] Provide a second element consisting of a second composition comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the second element, of at least one homopolyamide or at least one long-chain copolyamide, as defined above, Assemble the elements of the object by means of welding or an adhesive where appropriate, to form the finished or semi-finished object.

[0155] According to one embodiment, the method for manufacturing a single-material object as defined above may in particular comprise the step of assembling the elements of the object by means of welding, or by insertion on a fir tree tail, by clipping, or bonding by means of a non-polyamide adhesive where appropriate, to form the finished or semi-finished object.

[0156] In one embodiment, the method defined above comprises an additional step, before assembly, of providing a third element consisting of a third composition comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the third element of at least one homopolyamide or at least one long-chain copolyamide, as defined above, or at least one copolyamide with amide units (Ba1) and polyether units (Ba2) or a mixture of the two.

[0157] In another embodiment, the method defined above comprises an additional step, before assembly, of providing a fourth after providing the third element consisting of a fourth composition comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the third element of at least one homopolyamide or at least one long-chain copolyamide, as defined above, or at least one copolyamide with amide units (Ba1) and polyether units (Ba2) or a mixture of the two.

[0158] In yet another embodiment, the method defined above comprises an additional step, before assembly, of providing n elements after providing the fourth element consisting of a composition n comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the third element of at least one homopolyamide or at least one long-chain copolyamide, as defined above, or at least one copolyamide with amide units (Ba1) and polyether units (Ba2) or a mixture of the two.

[0159] In another embodiment, the method defined above comprises at least one additional step after assembly.

[0160] Said additional step, after assembly, may be a step of mounting on a vehicle and a first commissioning by storing, distributing or transporting the desired fluid.

[0161] According to another aspect, the present invention relates to a method of recycling the object as defined above, comprising the steps of: (a) providing the used object,

[0162] (b) optionally separation of the elements of the object which are not recyclable in said process,

[0163] (c) optionally cleaning the used object from step (a) or (b),

[0164] (d) optionally first crushing of the used object from step (a) or (b), or from step (c) when the cleaning of step (c) is carried out in order to obtain a first crush,

[0165] (e) optionally washing of the first ground material when the cleaning of step (c) is not carried out,

[0166] (f) crushing the used object from step (a) and / or (b) and / or (c) and / or (d) and / or (e) in order to obtain a first ground material or a second ground material in the case where a first crushing from step (d) has been carried out,

[0167] (g) optionally heating the ground material from step (f) until it melts and granulates,

[0168] (h) optionally compounding and granulation,

[0169] (i) extrusion or injection to manufacture an object.

[0170] The first and / or second grinding may take place before or after cleaning.

[0171] Cleaning (or decontamination) is necessary in the case of transport, distribution or storage of a liquid fluid but it is unnecessary in the case of transport, distribution or storage of a gas such as hydrogen or air.

[0172] Cleaning is carried out by means of compressed air, in particular under pressure, or by means of hot water or steam from said structure.

[0173] Compressed air cleaning removes non-polymeric particles such as soil, sand or dust from the used object.

[0174] Cleaning with hot water or steam makes it possible to solubilize and at least partially remove the water-soluble substances from said used object in order to obtain the other constituents of said used object.

[0175] The temperature of hot water or water vapor is between 70°C and 150°C, particularly between 70°C and 120°C.

[0176] Hot water can have a pH between 1 and 12.

[0177] The compounding step (h) allows the addition of an impact modifier and / or a filler and / or an additive and / or a plasticizer, depending on the characteristics of the product from step (f) or (g) after analysis of said product.

[0178] If step (h) is carried out, then the material obtained after said step (h) is in the form of granules to be subsequently extruded or injected.

[0179] The expression "used object" designates an object which is no longer new, which has already been used or which has already been used but in no case designates a post-industrial object which would be recycled without having been used or which has not been used. In another embodiment, the present invention relates to a recycling method as defined above, further comprising the step of:

[0180] (j) Addition of new material to the ground material of the used object before or after step (f) or after step (g).

[0181] The term new material refers to another polymer, in particular another polyamide, in particular a polyamide with a C / N < 8, as well as fillers and additives.

[0182] According to yet another aspect, the present invention relates to a recycled polyamide composition capable of being obtained by the process as defined above.

[0183] According to yet another aspect, the present invention relates to a composition comprising by weight: from 15 to 100%, in particular from 30 to 100%, advantageously from 50 to 99% of recycled polyamide from the objects defined above, from 0 to 70% of virgin polyamides chosen from homopolyamides, in particular having a C / N ratio greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10, copolyamides, in particular having a C / N ratio greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10, and PEBAs, advantageously the virgin polyamide is a homopolyamide, in particular having a C / N ratio greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10, from 0 to 65%, in particular from 0 to 35% of virgin or recycled fillers from the objects defined above,

[0184] 0 to 30% shock modifier

[0185] 0 to 5% of additives, said recycled polyamide having functions resulting from oxidation reactions chosen from primary amide functions, nitriles, methyl groups at the end of the chain, alkenes, formamides, imides, carboxylic acids and alcohols and their mixtures, in a molar ratio relative to the amide functions higher than that of the same polyamide constituting an unused object which has never been used.

[0186] In particular, according to the invention, the functions resulting from oxidation reactions may be present in the recycled polyamide of the invention in a molar ratio relative to the secondary amide functions at least 10% higher, for example at least 100% higher, for example at least 150% higher, for example at least 300% higher, compared to that of the same virgin polyamide elastomer.

[0187] When using a single-material object, new species resulting from oxidation mechanisms, in particular amide functions and / or methylene alpha to said amide functions, such as imide functions, carboxylic acids, primary amides and alcohols appear in the polyamides constituting said tubes, connectors or reservoirs.

[0188] These functions appear due to UV radiation or heat or due to a reaction with a compound with which the object is in contact. For example, gasoline, sunscreen, lubricants, etc.

[0189] These functions can be detected by infrared or NMR spectrometry.

[0190] Thus the absorption band from 1700 to 1740 cm-1 corresponds to an imide, that from 1680 to 1720 cm-1 to the carbonyl of the carboxylic acid and that from 3580 to 3670 cm-1 corresponds to the alcohol function of the carboxylic acid.

[0191] The absorption band from 3580 to 3670 cm-1 corresponds to the free alcohol function.

[0192] The amide function is characterized on the one hand by a pair of absorption bands from 3100 to 3500 cm-1 and from 1560 to 1640 cm-1 which corresponds to the NH group of the amide and on the other hand by the absorption band from 1650 to 1700 cm-1 which corresponds to the carbonyl group of the amide.

[0193] In a first variant, said composition comprises by weight: from 50 to 70% of recycled polyamide from the mono-material objects defined above, from 30 to 50% of virgin polyamides chosen from homopolyamides, in particular long chain, copolyamides, in particular long chain, and PEBA, advantageously the virgin polyamide is a homopolyamide, 0 to 30% of impact modifier,

[0194] 0 to 5%, in particular 0.1 to 5% of additives, the sum of the constituents being equal to 100%.

[0195] In a second variant, said composition comprises by weight: from 30 to 50% of recycled polyamide from the mono-material objects defined above, from 0 to 65% of virgin polyamides chosen from homopolyamides, in particular long chain, copolyamides, in particular long chain, and PEBA, advantageously the virgin polyamide is a homopolyamide, in particular long chain, 0 to 30% of impact modifier, from 5 to 65% of fillers, in particular from 5 to 35% of fillers,

[0196] 0 to 5%, in particular 0.1 to 5% of additives, the sum of the constituents being equal to 100%.

[0197] In a third variant, said composition comprises by weight: from 60 to 80% of recycled polyamide from the mono-material objects defined above, from 0 to 20% of virgin polyamides chosen from homopolyamides, in particular long chain, copolyamides, in particular long chain, and PEBA, advantageously the virgin polyamide is a homopolyamide, in particular long chain, 0 to 30% of impact modifier from 20 to 40% of fillers,

[0198] 0 to 5%, in particular 0.1 to 5% of additives, the sum of the constituents being equal to 100%.

[0199] In a fourth variant, said composition comprises by weight: from 40 to 60% of recycled polyamide from the mono-material objects defined above, from 0 to 20% of virgin polyamides chosen from homopolyamides, in particular long chain, copolyamides, in particular long chain, and PEBA, advantageously the virgin polyamide is a homopolyamide, in particular long chain,

[0200] 0 to 30% shock modifier, 40 to 60% fillers,

[0201] 0 to 5%, in particular 0.1 to 5% of additives, the sum of the constituents being equal to 100%.

[0202] In one embodiment, in said compositions of this other aspect and its four variants, the term "comprises" is replaced by the term "consisting of".

[0203] The compositions of these four variants and their embodiments are compositions particularly suitable for the embodiment in which the single-material object defined above is characterized in that only one of the two compositions comprises a filler, the other being devoid of it.

[0204] In one embodiment, said molar ratio of the functions resulting from oxidation reactions relative to the secondary amide functions is from 0.0001 to 0.3.

[0205] Concentrations can be measured by proton NMR in dichloromethane-d2, adding HFIP (hexafluoroisopropanol) to solubilize the polyamide.

[0206] In a first variant, said molar ratio of imide functions relative to secondary amide functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.05.

[0207] In one embodiment of this first variant, said molar ratio of imide functions relative to secondary amide functions is from 1 / 1000 to 1 / 100, in particular from 1 / 1000 to 1 / 300, in particular from 1 / 1000 to 1 / 500, more particularly from 1 / 1000 to 1 / 750.

[0208] In another embodiment of this first variant, said molar ratio of imide functions relative to secondary amide functions is from 1 / 750 to 1 / 20, in particular from 1 / 750 to 1 / 50, in particular from 1 / 750 to 1 / 100, more particularly from 1 / 750 to 1 / 300, in particular from 1 / 750 to 1 / 500.

[0209] In yet another embodiment of this first variant, said molar ratio of imide functions relative to secondary amide functions is from 1 / 500 to 1 / 20, in particular from 1 / 500 to 1 / 100, in particular from 1 / 750 to 1 / 300.

[0210] In yet another embodiment of this first variant, said molar ratio of imide functions relative to secondary amide functions is from 1 / 300 to 1 / 20, in particular from 1 / 300 to 1 / 50, in particular from 1 / 300 to 1 / 100.

[0211] In a second variant, said molar ratio of carboxylic acid functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.05.

[0212] In one embodiment of this second variant, said molar ratio of carboxylic acid functions relative to secondary amide functions is from 1 / 5000 to 1 / 20, in particular from 1 / 3000 to 1 / 25, in particular from 1 / 3000 to 1 / 50, very advantageously from 1 / 500 to 1 / 15.

[0213] In one embodiment of this second variant, said molar ratio of carboxylic acid functions relative to secondary amide functions is from 1 / 1000 to 1 / 100, in particular from 1 / 500 to 1 / 100, in particular from 1 / 400 to 1 / 100, more particularly from 1 / 300 to 1 / 100.

[0214] In a third variant, said molar ratio of alcohol functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.05.

[0215] In an embodiment of this third variant, said molar ratio of alcohol functions relative to secondary amide functions is from 1 / 1000 to 1 / 20 and advantageously from 1 / 1000 to 1 / 25, very advantageously from 1 / 200 to 1 / 50.

[0216] In an embodiment of this third variant, said molar ratio of alcohol functions relative to secondary amide functions is from 1 / 1000 to 1 / 200, in particular from 1 / 1000 to 1 / 300, in particular from 1 / 1000 to 1 / 400, more particularly from 1 / 1000 to 1 / 500.

[0217] In a fourth variant, said molar ratio of primary amide functions relative to secondary amide functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.05.

[0218] In an embodiment of this fourth variant, said molar ratio of primary amide functions relative to secondary amide functions is from 1 / 500 to 1 / 15, in particular from 1 / 400 to 1 / 15, in particular from 1 / 300 to 1 / 15, more particularly from 1 / 200 to 1 / 15, in particular from 1 / 100 to 1 / 15. In a fifth variant, said molar ratio of nitrile functions relative to secondary amide functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.05.

[0219] In a sixth variant, said molar ratio of methyl functions at the end of the chain relative to the secondary amide functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.05.

[0220] It is obvious that depending on the single-material objects used and the exposure to which they have been subjected, one or more functions resulting from oxidation reactions may be present.

[0221] The composition also advantageously comprises stabilizer residues chosen from phenols, quinones, stylbenequinone and phosphite.

[0222] The recycled polyamide advantageously comprises alkyl chain ends with a carbon number (between 1 and 18) higher than that of a virgin PA. Advantageously, the rate of alkyl chain ends is between 1 ppm and 0.5%.

[0223] According to another aspect, the present invention relates to the use of a composition as defined above for the manufacture of objects, in particular single-material objects.

[0224] Said single-material object thus manufactured from used single-material object can itself be recycled according to the method of the invention at least once, in particular from 1 to 10 times.

[0225] According to another aspect, the present invention relates to the use of the composition as defined above for the manufacture of objects, in particular single-material objects.

[0226] According to another aspect, the present 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 a fluid, in particular for a device with a thermal or electric engine such as an airplane, a drone, an aircraft, a truck or an automobile.

[0227] In one embodiment, said fluid is chosen from hydrogen and a coolant.

[0228] EXAMPLES

[0229] The examples in Tables 1, 2 and 3 below are ground and then granulated using a twin-screw extruder. [Table 1]

[0230] [Table 2]

[0231] [Table 3]

[0232] The injected parts 1, 2, 3, 4, 5 and 6 are connectors.

[0233] Extruded parts 1, 2, 3, 4, 5 and 6 are single-layer tubes for transporting coolant.

[0234] PA U BESNO TL: Arkema

[0235] PA 11 KNO: Arkema Orevac IM 800: SK Functional polymers

[0236] Stabilizers: 0.5% Lowinox 44B25 (SI group) and 0.2% irgafos 168 (BASF)

[0237] HDPE: High-density polyethylene 5502: Total Energy

[0238] PA 6 Ultramid B27: BASF

[0239] Fiberglass: CS 7928: Lanxess Deutschland GMBH

[0240] Objects EC1, El 1, EC2, E 12, EC3, and E 13 were ground into ground material with 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 in order to obtain granules to evaluate the properties obtained during the second life of the material.

[0241] The granules thus obtained are then injected using a Battenfeld BA800 CDC press to produce ISO 527 IA test pieces and ISO 179 impact bars. The following parameters were applied during injection:

[0242] - Sheath temperature: 270°C.

[0243] - Nozzle temperature: 290°C.

[0244] - Mold temperature: 40°C.

[0245] - Cycle time: 60 seconds.

[0246] The impact resistance was determined according to ISO 179-1: 2010 / leA (Charpy impact) on 5 bars measuring 80mm x 10mm x 4mm, V-notched, at a temperature of -30°C + / -2°C on dry samples.

[0247] Elongation at break was carried out on ISO 527 IA specimens.

[0248] The results are presented in Table 4 and 5.

[0249] [Table 4]

[0250] [Table 5]

[0251] The above examples show that the properties obtained after recycling the object according to the invention are better and therefore that it can be recycled to manufacture new high-performance objects. In addition, the evaluation of the cold impact resistance shows that the objects of the invention have better properties after recycling.

[0252] Examples EC1 and Eli include impact modifier (Orevac IM800) and are particularly suitable for applications where impact resistance, particularly cold, is required.

[0253] Examples EC2 and E 12 include fiberglass and are particularly suitable where pressure resistance is required.

[0254] The EC3 and EI3 examples allow a compromise to be achieved between impact, elongation at break and a fairly high tensile modulus (compared to EC1 and Eli).

[0255] In all three cases, the compositions according to the invention make it possible to achieve better properties and therefore greater durability of the objects.

Claims

CLAIMS 1. Single-material object, in particular recyclable, consisting mainly of long-chain polyamide comprising at least two elements: - at least one first element consisting of at least one extruded or blown extruded part intended for the transport, distribution and / or storage of a fluid, in particular chosen from a tube and a reservoir, comprising at least one layer consisting of a first composition comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the first element, of at least one homopolyamide or at least one copolyamide, said at least one homopolyamide or at least one copolyamide of the first composition having a C / N ratio greater than or equal to 8, in particular greater than or equal to 9, particularly greater than or equal to 10, said at least one homopolyamide and said at least one copolyamide representing, independently of one another, a repeating unit chosen from a unit obtained from the polycondensation of at least one C4-C36 amino acid,a unit obtained from the polycondensation of at least one C4-C3s lactam and an XY unit obtained from the polycondensation of: at least one diamine, said diamine being chosen from a linear or branched aliphatic diamine, a cycloaliphatic diamine and a semi-arylaliphatic diamine or a mixture thereof, and at least one dicarboxylic acid, said diacid being chosen from: an aliphatic diacid, a cycloaliphatic diacid and an aromatic diacid or a mixture thereof, said diamine and said diacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, - at least one second element consisting of at least one injected part consisting of a second composition comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the second element, of at least one homopolyamide or at least one copolyamide as defined above for the first composition, and said first and second elements being able to adhere at least partially to each other.

2. Single-material object according to claim 1, characterized in that it is chosen from an automobile, truck, aircraft and drone part.

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

4. Single-material object according to one of claims 1 to 3, characterized in that only one of the two compositions comprises a filler, the other being devoid of it.

5. Single-material object according to one of claims 1 to 4, characterized in that it is mainly made up of long-chain aliphatic polyamide or a mixture of elements made up of long-chain aliphatic and semi-aromatic polyamide.

6. Single-material object according to one of claims 1 to 5, characterized in that the first composition and the second composition comprise the same polyamide, in particular a PAU, PA12, PA1010, PA1012, PA610 and PA612.

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

8. Single-material object according to one of claims 1 to 5, characterized in that the difference in C / N between 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 is less than or equal to 3, in particular less than or equal to 2, in particular less than or equal to 1.

9. Single-material object according to one of claims 1 to 5, characterized in that said at least one homopolyamide or said at least one copolyamide of the first composition and said at least one homopolyamide or said at least one copolyamide of the second composition comprise a monomer having an identical C / N.

10. Single-material object according to claim 9, characterized in that said monomer is identical in each composition.

11. Single-material object according to one of claims 1 to 10, characterized in that the first and second elements adhere to each other by welding, insertion on a fir tree tail, clipping, or bonding using a non-polyamide adhesive in a content of 0.01% to 10% by weight, in particular 0.1% to 4% by weight relative to the total mass of the object or are introduced into each other.

12. Single-material object according to 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 with amide units (Ba1) and polyether units (Ba2) or a mixture thereof.

13. Single-material object according to claim 12, characterized in that it comprises up to 50 elements, in particular from 3 to 50 elements, in particular from 5 to 30 elements, in particular from 10 to 30 elements.

14. Method for manufacturing a single-material object according to one of claims 1 to 13, comprising the steps consisting of: Providing a first element consisting of a first composition comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the first element of at least one homopolyamide or at least one long-chain copolyamide, as defined above, Providing a second element consisting of a second composition comprising by weight at least 30%, in particular at least 50%, particularly at least 70%, more particularly at least 90%, relative to the total weight of the second element, of at least one homopolyamide or at least one long-chain copolyamide, as defined above, Assemble the elements of the object using welding or adhesive where appropriate, to form the finished or semi-finished object.

15. Method for recycling the object as defined in one of claims 1 to 13, comprising the steps consisting of: (a) supply of the used item, (b) optionally separation of the elements of the object which are not recyclable in said process, (c) optionally cleaning the used object from step (a) or (b), (d) optionally first crushing of the used object from step (a) or (b), or from step (c) when the cleaning of step (c) is carried out in order to obtain a first crush, (e) optionally washing of the first ground material when the cleaning of step (c) is not carried out, (f) crushing the used object from step (a) and / or (b) and / or (c) and / or (d) and / or (e) in order to obtain a first ground material or a second ground material in the case where a first crushing from step (d) has been carried out, (g) optionally heating the ground material from step (f) until it melts and granulates, (h) optionally compounding and granulation, (i) extrusion or injection to manufacture an object.

16. The recycling method of claim 15, further comprising the step of: (j) Addition of new material to the ground material of the used object before or after step (f) or after step (g).

17. Recycled polyamide composition obtainable by the process according to claims 15 to 16.

18. Composition comprising by weight: from 15 to 100%, in particular from 30 to 100%, advantageously from 50 to 99% of recycled polyamide from the objects defined in one of claims 1 to 13, from 0 to 70% of virgin polyamides chosen from homopolyamides, in particular having a C / N ratio greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10, copolyamides, in particular having a C / N ratio greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10, and PEBAs, advantageously the virgin polyamide is a homopolyamide, in particular having a C / N ratio greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10, from 0 to 65%, in particular from 0 to 35% of virgin or recycled fillers from the objects defined in one of claims 1 to 8, 0 to 30% shock modifier, 0 to 5% of additives, said recycled polyamide having functions resulting from oxidation reactions chosen from primary amide functions, nitriles, methyl groups at the end of the chain, alkenes, formamides, imides, carboxylic acids and alcohols and their mixtures, in a molar ratio relative to the amide functions higher than that of the same polyamide constituting an unused object which has never been used.

19. Composition according to claim 18, characterized in that said molar ratio of the functions resulting from oxidation reactions relative to the secondary amide functions is from 0.0001 to 0.

3.

20. Composition according to one of claims 18 to 19, characterized in that said molar ratio of the imide functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.

05.

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

05.

22. Composition according to one of claims 18 to 21, characterized in that said molar ratio of the alcohol functions relative to the secondary amide functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.

05.

23. Composition according to one of claims 18 to 22, characterized in that said molar ratio of the primary amide functions relative to the secondary amide functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.

05.

24. Composition according to one of claims 18 to 23, characterized in that said molar ratio of the nitrile functions relative to the secondary amide functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.

05.

25. Composition according to one of claims 18 to 24, characterized in that said molar ratio of the methyl functions at the end of the chain relative to the secondary amide functions is from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.

05.

26. Use of the composition according to one of claims 17 to 25 for the manufacture of objects, in particular single-material objects.

27. Use of a single-material object as defined in one of claims 1 to 13, for the manufacture of a system for transporting, distributing or storing a fluid, in particular for a device with a thermal or electric motor such as an airplane, a drone, an aircraft, a truck or an automobile.

28. Use of a single-material object according to claim 27, characterized in that said fluid is chosen from hydrogen and a cooling liquid.

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