FR3141469A1 - Recyclable single-material objects comprising at least two elements - Google Patents

Abstract

The present invention relates to a mono-material object comprising at least two elements: at least a first element consisting of a first composition comprising by weight at least 30% relative to the total weight of the first element, of at least one homopolyamide or 'at least one long-chain copolyamide, a copolyamide with amide units (Ba1) and polyether units (Ba2) being excluded from said first composition, at least one second element consisting of a second composition comprising by weight at least 30% per relative to the total weight of the second element, of a copolyamide with amide units (Ba1) and polyether units (Ba2), said first and second elements being able to adhere at least partially to one another, said at least one homopolyamide or at least one long-chain copolyamide of the first composition having a C/N ratio greater than or equal to 8 and said copolyamide of the second composition having a C/N ratio of the unit (Ba1) greater than or equal to 6, in particular greater than or equal to 8, said object being excluding a single-layer or multi-layer structure for the transport, distribution or storage of a fluid.

Description

Recyclable single-material objects comprising at least two elements

This patent application concerns recyclable mono-material 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 mono-materials.

The circular economy makes it possible to limit waste production, the depletion of the planet's resources and environmental impact. We are currently seeking in particular to produce objects using materials which will have sufficient properties after recycling to allow their use for high performance applications and not only for lower performance applications such as street furniture or roads.

In the context of sustainable consumption and production patterns, the suitability for recycling of frequently replaced items such as sporting goods and E&E articles and the quality of the resulting recycling products is of particular importance. However, the performance requirements are particularly high for these articles.

It is essential to design items such as sporting goods and E&E items so that they can be recycled to produce a material with high performance. It is also important that the products used to make objects are stable enough to be recycled safely. When thermoplastic polyurethanes (TPU) are recycled, the formation of isocyanate can be observed in FTIR. Isocyanates are dangerous compounds, CMR…

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 up of the same thermoplastic base material. However, it appears that there remain difficulties in that the recycling product thus obtained has limits in terms of performance due to the fact that the density of the shoe parts differs depending on their respective function.

Patent application WO 2020/201370 A1 proposes a method for recycling such shoes in which the shoe is crushed and then melted. This document focuses, like the previous one, on thermoplastic polyurethanes (TPU). This international application indicates that TPU degrades with recycling cycles.

Application US 2017/0151470 A1 concerns a ball, in particular a football, a manufacturing process and the recycling of the ball. The balloon is made up of a bladder, an intermediate layer and an outer layer, the bladder and the two layers being made up of a majority component by weight of a material of a first class of material chosen from polyurethane, polyvinyl chloride, polyethylene, polyamide and polypropylene.

International application WO 2021/148148 A1 relates to a lined article of clothing which comprises an outer layer, an inner layer and a lining between the two layers.

Each layer contains a majority of a material from the same family chosen from thermoplastic polymers, in particular a recycled polyester or a virgin polymer chosen from thermoplastic polyurethanes (TPU), polyamides (PA), polyethylene terephthalate (PET ) or polybutylene terephthalate (PBT). Polyesters have the disadvantage of being very sensitive to hydrolysis.

The invention therefore aims to propose a mono-material object whose composition is studied so as to enable the recycling of a composition capable of being used for applications requiring high performance.

However, it has been demonstrated that the exclusive combination (excluding additives and fillers) in a mono-material object of a polyamide fraction and a polyether block amide fraction (PEBA) allows better maintenance of properties during recycling.

Indeed, the presence in the composition of polyamides provides in particular good resistance to aging and therefore to the life of the object and its recycling process. For its part, the presence of PEBA, more flexible, contributes to improving the mechanical resistance of the object throughout its life, before and after recycling.

Also, according to a first aspect, the invention relates to a single-material object comprising at least two elements:

- at least one 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, at least one homopolyamide or at least one long-chain copolyamide,

said at least one homopolyamide and said at least one long-chain 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-C36 lactam and an XY pattern obtained from the polycondensation:

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

of at least one dicarboxylic acid, said diacid being chosen from:

an aliphatic diacid, a cycloaliphatic diacid and an aromatic diacid,

said diamine and said diacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms,

a copolyamide with amide units (Ba1) and polyether units (Ba2) being excluded from said first composition,

- at least one 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, a copolyamide with amide units (Ba1) and polyether units (Ba2)

said first and second elements being able to adhere at least partially to one another,

said at least one homopolyamide or at least one long-chain copolyamide of the first composition 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 said copolyamide of the second composition having a C/N ratio of the amide unit (Ba1) greater than or equal to 6, in particular greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10,

said object being excluding a single-layer or multi-layer structure for the transport, distribution or storage of a fluid.

The inventors have therefore unexpectedly found that the exclusive combination (excluding additives) in a mono-material object of a particular polyamide fraction (or element), namely long-chain polyamides and a fraction (or element) of copolyamide with a particular polyether block amide unit (PEBA), namely PEBAs having a C/N ratio of the amide unit (Ba1) greater than or equal to 6, in particular greater than or equal to 8, in particular greater than or equal to 9, in particular greater or equal to 10, allows better maintenance of properties during recycling.

Indeed, the long-chain polyamides in one of the two compositions and the copolyamides with a particular polyether block amide (PEBA) unit in the other composition present the best compromise and in particular provide good resistance to aging and therefore to the life of the object and its recycling process. They can also be recycled safely.

The recycled compositions also have the advantage of having a low density, good elastic return, good fatigue resistance, good impact resistance, good mechanical properties in traction, good dimensional stability, a stable modulus between -20°C and 30°C as well as good chemical resistance, in particular good resistance to hydrolysis.

The C/N ratio corresponds to the number of carbon atoms per nitrogen atom in the polyamide or copolyamide.

By “mono-material object” we must understand an object consisting mainly of the same material, in this case a long-chain polyamide in one of the two compositions and a polyamide in the pattern (Ba1) having a C/N ratio of pattern (Ba1) greater than or equal to 6, in particular greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10 in the other composition.

In a first variant, the mono-material objects can be without being limited to these:

An electronic item, in particular a watch, a phone case, headphones, earphones, a speaker, a keyboard, a mouse, a phone charger,

an article of clothing, in particular a jacket, pants, t-shirt, socks

an optical article, in particular prescription glasses, sunglasses, children's glasses, sports glasses and a ski mask, augmented reality/virtual reality glasses.

a household appliance, in particular a small household appliance, a household appliance accessory (bowl, mixing paddle, food container), a water bottle, a food container,

a cosmetic item, in particular cosmetic packaging such as a bottle, a perfume, makeup packaging, skincare packaging, a presentation item, a hairbrush,

a sporting item, in particular a surfboard (and its accessories such as leash or fins), a bicycle, bicycle item such as saddle or pedal, a helmet, a ski boot, skis, poles ski, a ski binding and a snowboard (excluding metal), a golf club, any type of racket in particular a tennis racket, protective equipment such as shin guard, elbow pad, etc., a hockey stick (on grass and ice), a roller skate, diving fins,

an item of luggage, in particular a suitcase, a backpack and a handbag

an item of stationery, especially pens.

a toy,

furniture, and

auto parts

(excluding a single-layer or multi-layer structure for the transport, distribution or storage of a fluid).

The expression "said object being excluding a single-layer or multi-layer structure for the transport, distribution or storage of a fluid" means that single-layer or multi-layer structures for the transport, distribution or storage of 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 are excluded from said object.

In one embodiment of this first variant, the mono-material objects correspond to all those described in the list of this first variant with the exception of at least one of those described in this same list and excluding of a single-layer or multi-layer structure for the transport, distribution or storage of a fluid.

It is obvious that at a minimum, said mono-material object corresponds to at least one of those described in said list of this first variant.

In a second variant, the mono-material objects can be an electronic article, a textile article, an optical article, a household appliance article, a cosmetic article, a sporting article, a stationery article, an article of luggage, a toy, furniture and automobile parts (excluding a single-layer or multi-layer structure for the transport, distribution or storage of a fluid).

In one embodiment of this second variant, the mono-material objects correspond to all those described in the list of this second variant with the exception of at least one of those described in this same list and excluding of a single-layer or multi-layer structure for the transport, distribution or storage of a fluid.

It is obvious that at a minimum, said mono-material object corresponds to at least one of those described in said list of this second variant.

In a third variant, the mono-material objects can be an electronic article, a textile article, an optical article, a household appliance article, a cosmetic article, a sporting article, a stationery article, an article of luggage, a toy, furniture.

In one embodiment of this third variant, the mono-material objects correspond to all those described in the list of this third variant with the exception of at least one of those described in this same list and excluding of a single-layer or multi-layer structure for the transport, distribution or storage of a fluid.

It is obvious that at a minimum, said mono-material object corresponds to at least one of those described in said list of this third variant.

Said object is excluding a single-layer or single-layer or multi-layer structure for the transport, distribution or storage of a fluid.

The term "fluid" includes any gas, in compressed form, in liquid form or even cryocompressed, and in particular hydrogen, natural gas, LPG, LNG, compressed air, nitrogen, oxygen, as well as a heat transfer fluid, in particular a refrigerant chosen from hydrocarbon compounds, hydrofluorocarbons, ethers, hydrofluoroethers, CO2, NH3, SO2 and fluoroolefins, in particular R134, R-1234yf or R-1234ze, in particular R-1234yf or R-1234ze, or even a gas used in automobiles, in particular air or a liquid used in automobiles, in particular water, an oil, a brake fluid, a urea solution, a coolant based on glycol, a transmission oil cooler (TOC), fuels, in particular diesel, gasoline, more particularly alcoholic gasoline or LPG.

In one embodiment, a shoe, a ball, a jacket, a seat in particular automobile, a toothbrush, or a backpack are excluded from the mono-material objects of the invention.

In one embodiment, at least 50% by weight of long-chain polyamide or long-chain copolyamide and polyamide with amide units (Ba1) in the copolyamide is present in each of the two elements relative to the total weight of the composition of each element.

In other words, the sum by weight of long-chain polyamide or long-chain copolyamide in the first element and polyamide with amide units (Ba1) in the second element is at least 50% relative to the total weight of the two compositions of each element.

In another embodiment, the matrix of each of the two elements (fillers and additives excluded) is made up of 60% by weight, advantageously 80% by weight, preferably 100% by weight of long-chain polyamide or long-chain copolyamide. chain for the first element or polyamide with amide patterns (Ba1) for the second element.

The term “element” designates each of the things whose combination, the union forms another thing, a whole, namely in the present invention a mono-material object.

In particular, an element designates a component, a component, a constituent, a piece, a part, a piece or unit which constitutes the mono-material object.

The expression “said first and second elements being able to adhere at least partially to one another” means that said first and second elements may or may not adhere to one another.

In one embodiment, said first and second elements do not adhere to each other.

In another embodiment, said first and second elements adhere to each other, at least partially, in particular completely.

The term “adheres” means that said first and second elements are attached to each other or applied against each other, at least partially and in particular by gluing, clipping, overmolding, thermoforming, screwing, sewing, welding or riveting.

It is obvious that said first composition which comprises a homopolyamide and a long-chain copolyamide can also comprise impact modifiers and/or plasticizers and/or fillers and/or additives.

It is obvious that said second composition which comprises a copolyamide with amide units (Ba1) and polyether units (Ba2) can also comprise impact modifiers and/or plasticizers and/or fillers and/or additives.

It is quite obvious that said third composition described below which comprises a homopolyamide and a long-chain copolyamide or a copolyamide with amide units (Ba1) and polyether units (Ba2) or a mixture of the two may also include impact modifiers and /or plasticizers and/or fillers and/or additives.

S’ acting of the homo polyamide and long chain copolyamide composition of first element and the third element .

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

Said long-chain homopolyamide and copolyamide 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.

In a first variant of the invention, the repetitive unit is a unit obtained from the polycondensation of at least one C4-C36 amino acid (or aminocarboxylic acid),

Advantageously, said aminocarboxylic acid comprises 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.

In a second variant of the invention, the repetitive unit is a unit obtained from the polycondensation of at least one C4-C36 lactam.

Advantageously, the lactam comprises 9 to 12 carbon atoms. It can thus be chosen from decanolactam (noted 10), undecanolactam (noted 11) and laurolactam or lauryllactam (noted 12), advantageously the lactam is lauryllactam.

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 several lactams.

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

XY repeating pattern

The repeating unit XY is a 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

of at least one dicarboxylic acid, said diacid being chosen from:

an aliphatic diacid, a cycloaliphatic diacid and an aromatic diacid or a mixture thereof,

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

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

In one embodiment, said diamine comprises 6 to 12 carbon atoms.

In the case where the diamine used to obtain this repetitive XY unit 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 last configuration, we speak of "branched aliphatic diamine". In the case where the main chain does not contain any substituent, the aliphatic diamine is called "linear aliphatic diamine".

Whether or not it contains methyl and/or ethyl substituents on the main chain, the aliphatic diamine used to obtain this repeating XY unit comprises from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, in particular from 9 to 18 carbon atoms.

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 mentioned can all be bio-resourced within the meaning of the ASTM D6866 standard.

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.

The cycloaliphatic diamine can 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 -dicyclohexyl-methane commonly referred to as "BMACM" or "MACM" (and denoted B below), p-bis(aminocyclohexyl)-methane commonly referred to as "PACM" (and denoted P below), isopropylidenedi(cyclohexylamine ) commonly referred to as "PACP", isophorone-diamine (noted IPD below) and 2,6-bis(amino methyl)norbornane commonly referred to as "BAMN" or bis(aminomethyl)cyclohexane commonly referred to as "BAC".

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).

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

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.

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

When the dicarboxylic acid is aliphatic and linear, it can be chosen from succinic acid (4), pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), acid 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.

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 the document EP 0 471 566.

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).

In one embodiment, the composition of the first element consists of a single homopolyamide.

In another embodiment, the homopolyamide of the composition of the first element is an aliphatic semi-crystalline homopolyamide.

A semi-crystalline homopolyamide, within the meaning of the invention, designates a material that 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 present a clear melting when passing its so-called melting temperature (Tf), and which becomes solid again when the temperature drops below its crystallization temperature.

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

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

The number average molecular mass Mn of said semi-crystalline homopolyamide is preferably in a range going 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. These Mn values can correspond at inherent viscosities greater than or equal to 0.8 as determined in m-cresol according to standard ISO 307:2007 but by changing the solvent (use of m-cresol in place of sulfuric acid and the temperature being 20°C).

The homopolyamide or copolyamide of the first composition and the patterned polyamide (Ba1) of the second composition may be identical or different.

In a first variant, only one of the two compositions includes a filler, the other being devoid of it.

In a second variant, the first composition and the second composition comprise the same polyamide, in particular a PA11.

In a third variant at least 10% by weight of the patterns, in particular at least 30% by weight, constituting said at least one homopolyamide or said at least one copolyamide of the first composition and said patterned polyamide (Ba1) of the second composition are identical, in particular said patterns are PA11 patterns.

In a fourth variant, the first composition and the second composition comprise the same polyamide, in particular a PA11.

In one embodiment of these four variants, said long-chain homopolyamide of the first composition is chosen from:

polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these or a copolyamide of these, in particular the PA11 and the PA12.

More particularly, said long-chain homopolyamide is chosen from: polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these or a copolyamide of these, in particular the PA11 and the PA12.

Even more particularly, said long-chain homopolyamide is polyamide 11.

In another embodiment of these four variants, said long-chain copolyamide is chosen from 11/10T, 11/BI, 11/B10, 11/BI/BT, 12/BI, 1010/B10 or a mixture of these this.

B corresponds to 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane commonly also called BMACM or MACM.

PACM corresponds to bis(p-aminocyclohexyl)-methane commonly also called P.

PACM is preferably PACM20 which is a mixture of isomers and contains approximately 20% of the trans-trans-PACM isomer or PACM50 which is a mixture of isomers and contains approximately 50% of the trans-trans-PACM isomer .

In yet another embodiment of these four variants, said polyamide with amide units (Ba1) of the second composition is chosen from:

polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these or a copolyamide of these, in particular the PA11 and the PA12.

More particularly, said polyamide with amide units (Ba1) of the second composition is chosen from: polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these or a copolyamide of these, in particular PA11 and PA12.

Even more particularly, said polyamide with amide units (Ba1) of the second composition is polyamide 11.

In yet another embodiment of these four variants, said long-chain homopolyamide of the first composition is chosen from:

polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these or a copolyamide of these, in particular the PA11 and the PA12, and

said polyamide with amide units (Ba1) of the second composition is chosen from:

polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these or a copolyamide of these, in particular the PA11 and the PA12.

More particularly, said long-chain homopolyamide is chosen from: polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these or a copolyamide of these, in particular the PA11 and the PA12, and

said polyamide with amide units (Ba1) of the second composition is chosen from: polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these ci or a copolyamide thereof, in particular PA11 and PA12.

Even more particularly, said long-chain homopolyamide is polyamide 11, and said polyamide with amide units (Ba1) of the second composition is polyamide 11.

In one embodiment, said first and second element are chosen from the following constituents: a textile, a film or textured film, a foam, an injected part, an extruded part, a 3D printed part, an adhesive, a non-woven , a veil and a part in consolidated thermoplastic composite.

In another embodiment, said mono-material object defined above is characterized in that it comprises at least two constituents defined above and which are different.

In yet another embodiment, said mono-material object as defined above is characterized in that it comprises at least at least three constituents defined above, in particular different.

As indicated above, the first element and the second element can adhere at least partially to each other. When they adhere to each other at least partially, the first and second elements adhere to each other by bonding using a non-polyamide adhesive in a content of 0.01% to 10 % by weight, in particular from 0.1% to 4% by weight relative to the total mass of the object.

Said adhesive can be a polyurethane, acrylic, acrylonitrile, polyester, polyisoprene, polybutadiene, vinyl adhesive, preferably it is chosen from a polyurethane, acrylic and polyester adhesive, advantageously it corresponds to a polyurethane adhesive.

Said mono-material object defined above may comprise at least one third element consisting of a third composition comprising by weight at least 50%, advantageously 70%, preferably 90% relative to the total weight of the third element of at least a homopolyamide or at least one long-chain copolyamide or a copolyamide with amide units (Ba1) and polyether units (Ba2) or a mixture of these.

In one embodiment, said first and second element are chosen from the following constituents: a textile, a film or textured film, a foam, an injected part, an extruded part, a 3D printed part, an adhesive, a non-woven , a veil and a part in consolidated thermoplastic composite.

In another embodiment, said mono-material object defined above is characterized in that it comprises at least two constituents defined above and which are different.

In yet another embodiment, said mono-material object as defined above is characterized in that it comprises at least three constituents defined above, in particular different.

As indicated above, the first element and the second element can adhere at least partially to each other. When they adhere to each other at least partially, the first and second elements adhere to each other by bonding using a non-polyamide adhesive in a content of 0.01% to 10 % by weight, in particular from 0.1% to 4% by weight relative to the total mass of the object.

Said mono-material object defined above may comprise at least a third element consisting of a third composition comprising at least one homopolyamide or at least one long-chain copolyamide or at least one copolyamide with amide units (Ba1) and polyether units (Ba2) or a mixture thereof, said at least one copolyamide with amide units (Ba1) and polyether units (Ba2) being as defined above.

In one embodiment, said third composition comprises by weight at least 50%, advantageously 70%, preferably 90% of at least one homopolyamide or at least one long-chain copolyamide or at least one copolyamide with amide units ( Ba1) and polyether patterns (Ba2) or a mixture thereof relative to the total weight of the third element.

Regarding the copolyamide with amide units (Ba1) and polyether units (Ba2) (PEBA) of the composition s of the second and third element

Poly ether 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 an pattern obtained from at least one lactam, or an X.Y pattern obtained from polycondensation:

- at least one diamine, said diamine being preferably chosen from a linear or branched aliphatic diamine or a mixture of these, and

- 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:

1) Polyamide sequences with diamine chain ends with polyoxyalkylene sequences with dicarboxylic chain ends.

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).

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.

The polyamide sequences with dicarboxylic chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.

Polyamide sequences with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting diamine.

Polyamide block and polyether block polymers can also include randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.

For example, polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted. We obtain a polymer essentially having polyether blocks, polyamide blocks of very variable length, but also the different reagents having reacted randomly which are distributed randomly (statistically) along the polymer chain.

Polyetherdiamine, polyamide precursors and a chain-limiting diacid can also be reacted. We obtain a polymer essentially having polyether blocks, polyamide blocks of very variable length, but also the different reagents having reacted randomly which are distributed randomly (statistically) along the polymer chain.

Amide motif (Ba1):

The amide unit (Ba1) corresponds to an aliphatic repeating unit as defined above.

Advantageously, the amide unit (Ba1) 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.

More advantageously, the amide unit (Ba1) is chosen from polyamide 11 and polyamide 12, in particular polyamide 11.

Polyether pattern (Ba2):

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 “of 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.

The composition of the invention is therefore devoid of polyetherdiamine triblock.

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.

The number average molecular mass (Mn) of the polyether blocks is advantageously between 200 and 4000 g/mole, preferably between 250 and 2500 g/mole, in particular between 300 and 1100 g/mole.

PEBA can be prepared by the following process:

- in a first step, the polyamide blocks (Ba1) are prepared by polycondensation

lactam(s), or

of the amino acid(s), or

the diamine(s) and the dicarboxylic acid(s); and where appropriate, the comonomer(s) chosen from lactams and alpha-omega aminocarboxylic acids;

in the presence of a chain limiter chosen from dicarboxylic acids; Then

- in a second step, the polyamide blocks (Ba1) obtained are reacted with polyether blocks (Ba2), in the presence of a catalyst.

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

The block formation reaction (Ba1) is usually carried out between 180 and 300°C, preferably from 200 to 290°C, the pressure in the reactor is established between 5 and 30 bars, and it is maintained for approximately 2 to 3 hours. The pressure is slowly reduced by bringing the reactor to atmospheric pressure, then the excess water is distilled off, for example, for an hour or two.

The polyamide with carboxylic acid ends having been prepared, the polyether and a catalyst are then added. The polyether can be added one or more times, the same for the catalyst. According to an advantageous form, the polyether is first added, the reaction of the OH ends of the polyether and the COOH ends of the polyamide begins with the formation of ester bonds and 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 reagents 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 followed 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.

We can also add during the synthesis, at the most appropriate time, one or more molecules used as an antioxidant, for example Irganox® 1010 or Irganox® 245.

We can also consider the PEBA preparation process such that all the monomers are added at the beginning, i.e. in a single step, to carry out the polycondensation:

lactam(s), or

of the amino acid(s), or

diamine(s) and dicarboxylic acid(s); and where applicable, the other or other polyamide comonomers;

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

- in the presence of blocks (Ba2) (polyether);

- in the presence of a catalyst for the reaction between the flexible blocks (Ba2) and the blocks (Ba1).

Advantageously, said dicarboxylic acid is used as chain limiter, which is introduced in excess relative to the stoichiometry of the diamine(s).

Advantageously, 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 is used as catalyst.

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

Generally speaking, the copolymers with known ether and amide units consist of linear and semi-crystalline aliphatic polyamide sequences (for example “Pebax” from Arkema).

In one embodiment, the copolyamide with amide units (Ba1) 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, such as determined according to ISO 1183-3:1999.

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

Concerning the mono-material object

It is made up of at least two elements: said at least one first element defined here as (E1) and said at least one second element defined here as (E2).

In a first variant, it is made up of two so-called elements: E1/E2.

The element E1 can adhere to the element E2 at least partially, in particular E1 and E2 adhere at least partially, in particular E1 and E2 adhere completely, in particular by means of an adhesive.

The single-material object is then chosen from those described above.

In a second variant, it is made up of more than two elements: E1/(E1)n/E2/(E2)m, n and m being between 0 and 5 and when n=0, then m is greater than 0 and when m=0, then n is greater than 0.

It is obvious that when two elements E1 or E2 are side by side, they can adhere at least partially to each other.

In one embodiment, the homopolyamides or copolyamides of element E1 and the copolyamides of element E2 comprise an identical monomer, for example 11-aminoundecanoic acid, in particular at least 5% by weight of a monomer identical with respect to the sum of the constituents of said homopolyamide or copolyamide, advantageously at least 10%, preferably at least 30%.

In one embodiment, the homopolyamides or copolyamides of element E1 and the copolyamides of element E2 comprise a monomer having an identical C/N ratio, in particular at least 5% by mass of a monomer having a C/N identical with respect to the sum of the constituents of said homopolyamide or copolyamide, advantageously 10%, preferably 30%.

In a third variant, it can be made up of more than two elements: said at least one first element defined here as (E1) and said at least one second element defined here as (E2) and said third element defined here as E3.

In one embodiment, it is made up of three elements: E1/E2/E3 or E1/E3/E2 or E3/E1/E2.

The element E1 can adhere to the element E2 at least partially, in particular E1 and E2 adhere at least partially, in particular E1 and E2 adhere completely, in particular by means of an adhesive.

The element E2 can adhere to the 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.

We would not depart from the scope of the invention if at least one other element E1 and/or E2 and/or E3 were present in said mono-material object.

In a first variant, the first element is of non-recycled origin.

In a second variant, the second element is of non-recycled origin.

In a third variant, the third element if present is of non-recycled origin.

In a fourth variant, the first element and the second element are of non-recycled origin.

In a fifth variant, the first element and the third element when present are of non-recycled origin.

In a sixth variant, the second element and the third element when present are of non-recycled origin.

In a seventh variant, the first element, the second element and the third element when present are of non-recycled origin.

In an eighth variant, the first element is of at least partially recycled origin.

In a ninth variant, the second element is of at least partially recycled origin.

In a tenth variant, the third element, if present, is of at least partially recycled origin.

In an eleventh variant, the first element and the second element are of at least partially recycled origin.

In a twelfth variant, the first element and the third element when present are of at least partially recycled origin.

In a thirteenth variant, the second element and the third element when present are of at least partially recycled origin.

In a fourteenth variant, the first element, the second element and the third element when present are of at least partially recycled origin.

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 or copolyamide with amide units ( Ba1) and polyether patterns (Ba2) of recycled origin.

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.

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 (Ba1) and polyether units (Ba2).

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 with polyether units (Ba2).

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

In another embodiment, the composition of the second element (E2) comprises a single copolyamide with amide units (Ba1) and polyether units (Ba2).

In another embodiment, the composition of the third element (E3) if present 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 copolyamide with amide units (Ba1) and polyether units (Ba2).

In another embodiment, the composition of the first element (E1) comprises a single homopolyamide or at least one long-chain copolyamide and the composition of the second element (E2) comprises a single copolyamide with amide units (Ba1) and polyether units (Ba2).

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

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

According to another aspect, the present invention relates to a method of manufacturing a single-material object as defined above, 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 a copolyamide with amide units (Ba1) and polyether units (Ba2), as defined above,

Assemble the elements of the object using adhesive if necessary, to form the finished or semi-finished object.

In one embodiment, the method defined above comprises an additional step before assembly of supplying 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 patterns (Ba2) or a mixture of the two.

In the case of a semi-finished object, a step of adding other elements not recyclable by the process of the invention but preferably easily separable from the elements of the invention: for example the electronics of a watch , is done.

According to yet another aspect, the present invention relates to a method of recycling an object as defined above, 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 grinding of the used object of step (a) or (b), or of step (c) when the cleaning of step (c) is carried out in order to obtain a first grind ,

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

(f) grinding 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 grinding of step (d) has been carried out,

(g) heating the ground material from step (f) until it melts,

(h) optionally compounding and

(i) extrusion or injection of the melt.

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

Cleaning is carried out using compressed air, in particular under pressure, or using hot water or steam from said structure.

Cleaning with compressed air makes it possible to remove non-polymeric particles such as earth, sand or dust from said used object.

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

The temperature of the hot water or water vapor is between 70°C and 150°C, in particular between 70°C and 120°C.

Hot water can have a pH between 1 and 12.

Compounding step (h) makes it possible to add an impact modifier and/or a filler and/or an additive and/or a plasticizer.

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

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. not used.

In another embodiment, the present invention relates to a recycling process as defined above, 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).

The term new material also designates another polymer, in particular another polyamide, in particular a polyamide with A C/N < 8 as fillers and additives.

Regarding additives:

The additive is optional and included from 0 to 20%, in particular from 0.1 to 5% by weight.

The additive is chosen from dyes, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, lubricants, flame retardants, natural waxes, impact modifiers, additives for marking laser, and their mixtures.

Regarding charges:

Concerning the fillers, these are reinforcing fibers, which are in particular fibers of mineral, organic or plant origin.

Said reinforcing fiber can be sized or unsized.

Said reinforcing fiber can therefore comprise up to 0.1% by weight of a material of an organic nature (thermosetting or thermoplastic resin type) called sizing.

Among the fibers of mineral origin, we can cite carbon fibers, glass fibers, basalt fibers or basalt-based fibers, silica fibers, or silicon carbide fibers for example. Among the fibers of organic origin, we can cite fibers based on thermoplastic or thermosetting polymer, such as semi-aromatic polyamide fibers, aramid fibers or polyolefin fibers for example. Preferably, they are based on an amorphous thermoplastic polymer and have a glass transition temperature Tg greater than the Tg of the polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is amorphous, or greater than the Tf of the polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is semi-crystalline. Among the fibers of plant origin, we can cite natural fibers based on flax, hemp, lignin, bamboo, silk in particular spider silk, sisal, and other cellulosic fibers, in particular viscose. These fibers of plant origin can be used pure, treated or coated with a coating layer, in order to facilitate adhesion and impregnation of the thermoplastic polymer matrix.

Preferably said reinforcing fiber is chosen from glass fibers, carbon fibers, basalt fibers and basalt-based fibers.

More advantageously, said reinforcing fiber is chosen from carbon fibers and glass fibers.

In one embodiment, the reinforcing fibers present in a) are glass fibers.

The glass fibers can be circular or non-circular in section.

A fiber with a circular section is defined as a fiber having at any point of its circumference a distance equal to the center of the fiber and therefore represents a perfect or almost perfect circle.

Any fiberglass that does not present this perfect or almost perfect circle is therefore defined as a fiber with a non-circular section.

Examples of fibers with a non-circular section, without being limited to these, are non-circular fibers, having for example an elliptical, oval or cocoon shape, star fibers, flake fibers, fibers flat, cruciform, a polygon and a ring.

Fiberglass can be:

- either with a circular section with a diameter of between 4 μm and 25 μm, preferably 4 to 15 μm.

- either with a non-circular section with a ratio L/D (L representing the largest dimension of the transverse section of the fiber and D the smallest dimension of the transverse section of said fiber) of 2 to 8, in particular 2 to 4. L and D can be measured by scanning electron microscopy (SEM).

Advantageously, the glass fibers are circular.

The glass fibers are in particular of type E, R, S2, or T. Advantageously the glass fibers are of type E.

In another embodiment, the charges are present from 0 to 65%.

In one embodiment, the fillers are recycled.

For fillers comprising glass, they may in particular be manufactured from industrial production waste or post-consumer glass.

Carbon fibers can, for example, come from cutting spools of expired long fibers, in particular carbon fibers for aeronautics.

Advantageously, the fillers are chosen from glass fibers, in particular circular, and carbon fibers, in particular glass fibers, in particular circular.

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

According to yet another aspect, the present invention relates to a composition comprising by weight:

from 30 to 100%, advantageously from 50 to 99% of recycled polyamide from the mono-material objects defined above,

from 0 to 70% 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,

from 0 to 65% load,

0 to 20% additives, in particular from 0.1 to 5%,

the sum of the constituents being equal to 100%,

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 before.

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

Said functions appear due to UV radiation or heat or due to a reaction with a compound with which said object is in contact. For example, gasoline, sunscreen, lubricants...

Said functions can be detected by infrared or NMR spectrometry.

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 acid carboxylic.

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

The amide function is characterized on the one hand by a pair of absorption bands from 3100 to 3500 cm-1 and from 15560 to 1640 cm-1 which corresponds to the NH group of the amide and on the other hand by the band d absorption from 1650 to 1700 cm-1 which corresponds to the carbonyl group of the amide.

In a first variant, said composition comprises by weight:

50 to 70% recycled polyamide from 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 20% additives, in particular from 0.1 to 5%,

the sum of the constituents being equal to 100%.

In a second variant, said composition comprises by weight:

30 to 50% recycled polyamide from 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,

from 5 to 60% load,

0 to 20% additives, in particular from 0.1 to 5%,

the sum of the constituents being equal to 100%.

In a third variant, said composition comprises by weight:

60 to 80% recycled polyamide from 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,

from 20 to 40% load,

0 to 20% additives, in particular from 0.1 to 5%,

the sum of the constituents being equal to 100%.

In a fourth variant, said composition comprises by weight:

40 to 60% recycled polyamide from 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,

from 40 to 60% load,

0 to 20% additives, in particular from 0.1 to 5%,

the sum of the constituents being equal to 100%.

In one embodiment, in said compositions of this other aspect and its four variants, the term “includes” is replaced by the term “consisting of”.

The compositions of these four variants and their embodiments are compositions in particular adapted to the embodiment in which the mono-material object defined above is characterized in that only one of the two compositions comprises a filler, the other being deprived of it.

In one embodiment, said molar ratio of functions resulting from oxidation reactions relative to secondary amide functions is comprised from 1/10,000 to 1/20.

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

In a first variant, said molar ratio of the imide functions is comprised from 1/1000 to 1/20, in particular from 1/500 to 1/20, in particular from 1/200 to 1/50.

In a second variant, said molar ratio of the carboxylic acid functions is from 1/5000 to 1/20, in particular from 1/3000 to 1/50, very advantageously from 1/500 to 1/15.

In a third variant, said molar ratio of the alcohol functions is between 1/1000 and 1/20 and advantageously between 1/1000 and 1/25, very advantageously between 1/200 and 1/50.

In a fourth variant, said molar ratio of the primary amide functions relative to the secondary amide functions is between 1/2000 and 1/20 and advantageously between 1/1000 and 1/100, very advantageously between 1/1000 and 1/500. .

In a fifth variant, said molar ratio of the nitrile functions relative to the secondary amide functions is between 1/1000 and 1/20 and advantageously between 1/500 and 1/15, very advantageously between 1/100 and 1/10.

In a fifth variant, said molar ratio of the methyl functions at the end of the chain relative to the secondary amide functions is from 1/5000 to 1/50 and advantageously from 1/2000 to 1/100, very advantageously from 1/1000 to 1/100. 1/200.

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

The composition also advantageously comprises residues of stabilizers chosen from phenols, quinones, stylbenequinones and phosphite.

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

According to another aspect, the present invention relates to the use of a composition as defined above for the manufacture of objects, in particular mono-materials.

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

Brief description of the figure:

There presents the CH2CO areas of the different secondary amide, primary amide and carboxylic acid functions in C13 NMR in a solvent mixture with an HFIP/CD2Cl2 ratio of 1/3.

Top spectrum: PA 11 from electronic watch case worn for five years on the arm all day and bottom spectrum: PA 11 based on 100% virgin material.

EXAMPLES

The case and bracelet of the EC1 and EI 1 electronic watches are assembled using screws. The percentages indicated are mass percentages. The screws were removed before recycling.

The compositions and their evaluation are presented in Table 1.

Electronic watch EI 1 EC1 Element 1: box AP 11 PA 11 70% 70% Item 2: Bracelet PEBA TPU 30% 30% Density 1.04 1.08 Modulus (MPa) 711 733

Objects EC1 and EI 1 were crushed into ground material having a size less than 30 mm then compounded in an 18 mm twin-screw extruder at a flow rate of 5 kg/h and a temperature of 250 ° C in order to obtain granules to evaluate the properties obtained during the second life of the material.

The granules thus obtained are then injected using a Battenfeld BA800 CDC press to manufacture ISO 527 1A test pieces. The following parameters were applied during the injection:

- Sheath temperature: 240°C.

- Nozzle temperature: 260°C.

- Mold temperature: 30°C.

- Cycle time: 60 seconds.

The tensile modulus at 23°C is measured according to the ISO 527-1A standard.

the density at 23°C is measured according to the ISO 1183-1 standard.

The objects of the invention make it possible to obtain, after recycling, compositions having lower densities for an equivalent module.

The examples above show that the properties obtained after recycling of the object according to the invention are better and therefore that it can be recycled to manufacture new high-performance objects.

Claims (23)

Single-material object comprising at least two elements:

• at least 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 at least one homopolyamide or at least one long-chain copolyamide,
  said at least one homopolyamide and said at least one long-chain copolyamide representing, independently of one another, a repeating unit chosen from a unit obtained from the polycondensation of at least one C ₄ -C ₃₆ amino acid, a pattern obtained from the polycondensation of at least one C ₄ -C ₃₆ lactam and an XY pattern obtained from the polycondensation:
  • 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
  • of at least one dicarboxylic acid, said diacid being chosen from:
    an aliphatic diacid, a cycloaliphatic diacid and an aromatic diacid,
    said diamine and said diacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms,
    a copolyamide with amide units (Ba1) and polyether units (Ba2) being excluded from said first composition,
• at least one 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 a copolyamide with amide units (Ba1) and polyether units (Ba2)

said first and second elements being able to adhere at least partially to one another,
said at least one homopolyamide or at least one long-chain copolyamide of the first composition 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 said copolyamide of the second composition having a C/N ratio of the unit (Ba1) greater than or equal to 6, in particular greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10,
said object being excluding a single-layer or multi-layer structure for the transport, distribution or storage of a fluid. Mono-material object according to claim 1, characterized in that it is chosen from an electronic article, a textile article, an optical article, a household appliance article, a cosmetic article, a sporting article, a stationery article, an article luggage, a toy, furniture and automobile parts. Single-material object according to claim 1 or 2, characterized in that only one of the two compositions comprises a filler, the other being devoid of it. Mono-material object according to Claim 1 to 3, 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 said patterned polyamide (Ba1) of the second composition are identical, in particular said patterns are PA11 patterns. Mono-material object according to Claim 1 to 4, characterized in that the first composition and the second composition comprise the same polyamide, in particular a PA11. Mono-material object according to one of claims 1 to 4, characterized in that said first and second element are chosen from the following constituents: a textile, a film or textured film, a foam, an injected part, an extruded part, a 3D printed part, an adhesive, a non-woven fabric, a veil and a consolidated thermoplastic composite part. Single-material object according to claim 6, characterized in that it comprises at least two constituents defined in claim 6 and which are different. Mono-material object according to claim 7, characterized in that it comprises at least at least three constituents defined in claim 6, in particular different. Mono-material object according to one of claims 1 to 8, characterized in that the first and the second element adhere to each other by bonding by means of a non-polyamide adhesive with a content of 0.01 % to 10% by weight, in particular from 0.1% to 4% by weight relative to the total mass of the object. Mono-material object according to one of claims 1 to 9, characterized in that it comprises at least a third element consisting of a third composition comprising
at least one homopolyamide or at least one long-chain copolyamide or at least one copolyamide with amide units (Ba1) and polyether units (Ba2) or a mixture thereof, said at least one copolyamide with amide units (Ba1) and with polyether units (Ba2) being as defined in claim 1. Method of manufacturing a single-material object according to one of claims 1 to 10, 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 in claim 1,
• 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
  a copolyamide with amide units (Ba1) and polyether units (Ba2), as defined in claim 1,
• Assemble the elements of the object using adhesive if necessary, to form the finished or semi-finished object.

Process for recycling the object as defined in one of claims 1 to 10, 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 grinding of the used object of step (a) or (b), or of step (c) when the cleaning of step (c) is carried out in order to obtain a first grind ,
• (e) optionally washing the first ground material when the cleaning of step (c) is not carried out,
• (f) grinding 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 grinding of step (d) has been carried out,
• (g) heating the ground material from step (f) until it melts,
• (h) optionally compounding and
• (i) extrusion or injection of the melt.

Recycling method according to claim 12, 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).

Recycled polyamide composition capable of being obtained by the process according to claims 12 to 13. Composition including by weight

• from 30 to 100%, advantageously from 50 to 99% of recycled polyamide from the objects defined in one of claims 1 to 10,
• from 0 to 70% 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, from 0 to 65% of charges
• 0 to 20% additives, in particular from 0.1 to 5%,

the sum of the constituents being equal to 100%,
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 before. Composition according to claim 15, characterized in that said molar ratio of functions resulting from oxidation reactions relative to secondary amide functions is comprised from 1/10,000 to 1/20. Composition according to Claim 15 to 16, characterized in that said molar ratio of the imide functions relative to the secondary amide functions is comprised from 1/1000 to 1/20, in particular from 1/500 to 1/20, in particular from 1/ 200 to 1/50. Composition according to one of claims 15 to 17, characterized in that said molar ratio of the carboxylic acid functions relative to the secondary amide functions is comprised from 1/5000 to 1/20, in particular from 1/3000 to 1/50 very advantageously ranging from 1/500 to 1/15. Composition according to one of claims 15 to 18, characterized in that said molar ratio of the alcohol functions relative to the secondary amide functions is from 1/1000 to 1/20 and advantageously from 1/1000 to 1/25, very advantageously ranging from 1/200 to 1/50. Composition according to one of Claims 15 to 19, characterized in that said molar ratio of the primary amide functions relative to the secondary amide functions is comprised from 1/2000 to 1/20 and advantageously comprised from 1/1000 to 1/100 very advantageously between 1/1000 and 1/500. Composition according to one of claims 15 to 20, characterized in that said molar ratio of the nitrile functions relative to the secondary amide functions is from 1/1000 to 1/20 and advantageously from 1/500 to 1/15, very advantageously ranging from 1/100 to 1/10. Composition according to one of claims 15 to 21, characterized in that said molar ratio of the methyl functions at the end of the chain relative to the secondary amide functions is from 1/5000 to 1/50 and advantageously from 1/2000 to 1 /100 very advantageously included from 1/1000 to 1/200. Use of the composition according to one of claims 14 to 22, for the manufacture of objects, in particular mono-materials.