FR3116019A1 - SINGLE-LAYER STRUCTURE BASED ON RECYCLED POLYAMIDE - Google Patents

Abstract

The present invention relates to a single-layer tubular structure intended for the transport of automotive fluids, in particular air, oil, water, a urea solution, a glycol-based coolant, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, consisting of: a layer (1) consisting of a composition mainly comprising at least one semi-crystalline aliphatic polyamide, said composition consisting of at least 50% recycled material originating from a single-layer and/or multi-layer tube having been intended for the transport of automotive fluids, in particular as defined above, said tube consisting of a composition which mainly comprises at least one polyamide, said at least one tube having undergone grinding and recompounding with reformulation to be able to be recycled, simple single grinding or bro yage and recompounding without reformulation being excluded.

Description

SINGLE-LAYER STRUCTURE BASED ON RECYCLED POLYAMIDE

Every year, several million motor vehicles fall out of use around the world. An end-of-life motor vehicle (VHU) contains many toxic and polluting products (liquid or solid): motor oil, battery, air conditioning fluid, explosive elements of airbags, etc. Treated in poor conditions, this waste can lead to soil and water pollution, as well as accidents. ELVs are therefore considered hazardous waste.

A large number of vehicle components can be recovered and recycled, in the form of second-hand spare parts or raw materials. Parts intended for reuse (headlights, indicators, engine, radiator, starter, bonnet, fenders, doors, etc.) are dismantled and stored for resale.

Non-recyclable carcasses and parts (ferrous and non-ferrous metals, plastics, glass, rubber, etc.) are crushed for recovery or landfill.

European Directive 2000/53/EC on end-of-life vehicles has set a reuse and recovery rate of 95% by weight per vehicle from 2015.

Only 5% of ultimate waste should therefore remain, i.e. waste which is not likely to be treated under the technical and economic conditions of the moment and which will be incinerated or evacuated to specific storage centres.

The 95% reused and recovered are subject to:

Energy recovery: use of waste (oils, tires, plastics, etc.) as means of energy production, by direct incineration with or without other waste;

Material recovery: Reuse or reuse: new use of a part that retains the same use and is not transformed, or Recycling: operation aimed at introducing materials from waste into the production cycle, in total or partial replacement of virgin material.

A motor vehicle contains a large number of pipes, in particular pipes intended for the transport of fluids such as air, oil (for example for cooling the automatic gearbox "TOC, Transmission Oil Cooler), water, a urea solution, a glycol-based coolant, a fuel such as gasoline, in particular bio-gasoline or diesel, in particular bio-diesel, or hydrogen.

These pipes can be monolayer and/or multilayer tubular structures, in particular based on polyamide(s).

When the motor vehicle is out of use, the various pipes present in it are generally very or too degraded to be able to be reused such as, in the form of a tube, without risk or without this leading to excessive use properties. degraded.

Indeed, the tubes, especially under the engine hood, are placed in a severe thermo-oxidative environment due to the heat released by the engine which can typically reach 150°C and the presence of air and therefore oxygen. Each increase in temperature of 10° C. typically results in a halving of the service life of the tubes as well as the degradation of certain additives of said tubes such as stabilizers.

In addition, a pipe for transporting a fuel, for example a pipe made of polyamide which contains a plasticizer, has lost most of its plasticizer when it reaches the end of its life and the polyamide constituting it initially present is depolymerized and/ or degraded and has lost most of its stabilizers, which prohibits its safe reuse.

Until now, the end-of-life automobile hose is not reused and is often incinerated, but this then contributes to global warming, the reduction of which is becoming one of the major challenges of the ^21st century.

In addition, several car manufacturers have the more or less long-term objective of recycling 100% of the vehicles they produce in order to achieve an environmental impact equal to zero.

Consequently, the supply of recycled pipe to these manufacturers becomes essential and then makes it possible to reduce the quantity of pipe to be thrown away or incinerated.

1. The present invention therefore relates to a single-layer tubular structure intended for the transport of automotive fluids, in particular air, oil, water, a urea solution, a glycol-based cooling liquid, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, consisting of a layer (1) consisting of a composition mainly comprising at least one semi-crystalline aliphatic polyamide, said composition consisting of at least 50% of recycled material originating from at least one monolayer and/or multilayer tube having been intended for the transport of fluids for automobiles, in particular as defined above, said tube consisting of a composition which mainly comprises at least one polyamide,

said at least one tube having undergone grinding and recompounding with reformulation to be able to be recycled,

simple single grinding or grinding and recompounding without reformulation being excluded.

The inventors have therefore surprisingly found that a layer based on polyamide and consisting of at least 50% recycled material allows the constitution of a single-layer tubular structure capable of transporting an automotive fluid, in particular air, oil, water, urea solution, glycol-based coolant, or a fuel such as gasoline, especially bio-gasoline or diesel, especially bio-diesel , or hydrogen, regardless of the type of fluid initially transported by the recycled single-layer and/or multi-layer tube constituting the layer in contact with the transported fluid, said single-layer structure having, against all odds, much better properties than those of the same tubular structure whose layer (1) based on polyamide and made up of at least 50% recycled material is of simply ground origin.

The term "fluid" means a gas or a liquid used in the automobile, in particular air, oil, water, a urea solution, a coolant based on glycol, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen.

Advantageously, said fluid designates fuels, in particular gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

The term “gasoline” designates a mixture of hydrocarbons resulting from the distillation of petroleum to which additives or alcohols such as methanol and ethanol may be added, alcohols being able to be the majority components in certain cases.

The expression “alcoholic gasoline” designates a gasoline in which methanol or ethanol has been added. It also designates an E95 type gasoline which does not contain any petroleum distillation product.

The expression “based on polyamide” means at least 50% by weight of polyamide in the layer.

The expression “a composition mainly comprising at least one polyamide…” means at least 50% by weight of said polyamide in the composition.

Regarding the layer (1)

Layer (1) is consisting of a composition mainly comprising at least one semi-crystalline aliphatic polyamide, said composition consisting of at least 50% recycled material originating from a single-layer and/or multi-layer tube having been intended for the transport of automotive fluids.

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" and is well known to those skilled in the art.

The term “polyamide” according to the invention denotes both a homopolyamide and a copolyamide.

The expression “semi-crystalline polyamide” within the meaning of the invention throughout the description denotes polyamides which have a melting temperature (Tm) and an enthalpy of fusion ∆H > 25 J/g, in particular > 40 J/g, in particular > 45J/g, as well as a glass transition temperature (Tg) as determined by DSC according to ISO 11357-1:2016 and ISO 11357-2 and 3:2013, at a heating rate of 20K/min.

Said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one lactam, or from the polycondensation of at least one amino acid, or from the polycondensation of at least one diamine Xa with at least one dicarboxylic acid Yb.

When said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one lactam, said at least one lactam can be chosen from a C6 to C18 lactam, preferably C10 to C18, more preferably C10 at C12. A C6 to C12 lactam is in particular caprolactam, decanolactam, undecanolactam, and lauryllactam.

When said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one lactam, it can therefore comprise a single lactam or several lactams.

Advantageously, said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of a single lactam and said lactam is chosen from lauryllactam and undecanolactam, advantageously lauryllactam.

When said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one amino acid, said at least one amino acid may be chosen from a C6 to C18 amino acid, preferably C10 to C18, more preferably C10 at C12.

A C6 to C12 amino acid is in particular 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid as well as its derivatives, in particular N-heptyl-11-aminoundecanoic acid.

When said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one amino acid, it can therefore comprise a single amino acid or several amino acids.

Advantageously, said semi-crystalline aliphatic polyamide is obtained from the polycondensation of a single amino acid and said amino acid is chosen from 11-aminoundecanoic acid and 12-aminododecanoic acid, advantageously 11-aminoundecanoic acid.

When said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one diamine Xa at C4-C36, preferentially C5-C18, preferentially C5-C12, more preferentially C10-C12, with at least one diacid Yb at C4-C36, preferably C6-C18, preferably C6-C12, more preferably C10-C12, then said at least one diamine at Xa is an aliphatic diamine and said at least one diacid Yb is an aliphatic diacid.

The diamine can be linear or branched. Advantageously, it is linear.

Said at least one C4-C36 diamine Xa can be chosen in particular from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylediamine, 1,8-octamethylediamine, 1,9-nonamethyldiamine, 1,10-decamethyldiamine, 1,11-undecamethyldiamine, 1,12-dodecamethyldiamine, 1,13-tridecamethyldiamine, 1,14-tetradecamethyldiamine, 1,16-hexadecamethyldiamine and 1 ,18-octadecamethylediamine, octadecenediamine, eicosanediamine, docosanediamine and diamines obtained from fatty acids.

Advantageously, said at least one diamine Xa is C5-C18 and chosen from 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylediamine, 1,8-octamethylediamine, 1,9-nonamethylediamine, 1,10-decamethyldiamine, 1,11-undecamethyldiamine, 1,12-dodecamethyldiamine, 1,13-tridecamethyldiamine, 1,14-tetradecamethyldiamine, 1,16-hexadecamethyldiamine and 1,18-octadecamethyldiamine.

Advantageously, said at least one C5 to C12 diamine Xa is chosen in particular from 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylediamine, 1,8-octamethylediamine, 1,9- nonamethylediamine, 1,10-decamethylediamine, 1,11-undecamethylediamine, 1,12-dodecamethylediamine.

Advantageously, said at least one C6 to C12 diamine Xa is chosen in particular from 1,6-hexamethylenediamine, 1,7-heptamethylediamine, 1,8-octamethylediamine, 1,9-nonamethylediamine, 1,10- decamethylediamine, 1,11-undecamethylediamine, 1,12-dodecamethylediamine.

Advantageously, the diamine Xa used is C10 to C12, in particular chosen from 1,10-decamethylediamine, 1,11-undecamethylediamine, 1,12-dodecamethylediamine.

Said at least one C4 to C36 dicarboxylic acid Yb can be chosen from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and diacids obtained from fatty acids.

The diacid can be linear or branched. Advantageously, it is linear.

Advantageously, said at least one dicarboxylic acid Yb is C6 to C18 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.

Advantageously, said at least one dicarboxylic acid Yb is C6 to C12 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid.

Advantageously, said at least one dicarboxylic acid Yb is C10 to C12 and is chosen from sebacic acid, undecanedioic acid, dodecanedioic acid.

When said aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one diamine Xa with at least one dicarboxylic acid Yb, it can therefore comprise a single diamine or several diamines and a single dicarboxylic acid or several dicarboxylic acids.

Advantageously, said aliphatic semi-crystalline polyamide is obtained from the polycondensation of a single diamine Xa with a single dicarboxylic acid Yb.

The expression "mainly comprising at least one aliphatic-type polyamide" means that said composition of layer (1) comprises at least 50% by weight of at least one aliphatic polyamide relative to the total weight of said composition.

Advantageously, said composition of the layer (1) comprises at least 60% by weight, in particular at least 70% by weight, in particular at least 80% by weight, more particularly at least 90% by weight of at least one aliphatic polyamide relative to the total weight of said composition.

Said composition of layer (1) consists of at least 50% recycled material from a single-layer and/or multi-layer tube that has been intended for the transport of automotive fluids.

This means either that the "at least one majority polyamide" of said composition corresponds in its entirety to what is referred to as "at least 50% of recycled material" or that at least 50% by weight of all the constituents of the composition are of recycled origin from single-layer pipe, or multi-layer pipe, or a mixture of single-layer and multi-layer pipe.

The recycled material can come from a single-layer and/or multi-layer tube, said single-layer and/or multi-layer tubes having been intended for the transport of automotive fluids. Said tube is therefore a used tube, that is to say that it has been used for at least one year for the transport of the said fluid defined above. Said monolayer tube consists of a composition comprising a semi-crystalline aliphatic polyamide and optionally impact modifiers and/or additives and/or plasticizers and/or antistatic fillers.

Said multilayer tube comprises at least one layer consisting of a composition comprising a semi-crystalline aliphatic polyamide and optionally impact modifiers and/or additives. It can therefore comprise other layers consisting of a thermoplastic polymer other than a semi-crystalline aliphatic polyamide, such as for example a polypropylene, a semi-aromatic polyamide or a poly ethylene vinyl alcohol (EVOH).

It is obvious that the single-layer tube can also be a mixture of single-layer tubes, that is to say for example two types of single-layer tubes each consisting of a different semi-crystalline aliphatic polyamide, for example a PA11 and a PA12 .

It is also obvious that the multilayer tube can also be a mixture of different types of multilayer tube, provided that at least one of the layers of one of the types of multilayer tube is made of a semi-crystalline aliphatic polyamide.

If the mixed tubes are incompatible with each other, then the addition of a second semi-crystalline aliphatic polyamide noted B and having an average number of carbon atoms per nitrogen atom noted C _B = Cc – 1, preferably C _B = Cc – 2 and preferably a third polyamide makes it possible to compatibilize them.

Said single-layer and/or multi-layer tube which has been intended for transporting automotive fluids and which is therefore used is crushed, recompounded and reformulated, in order to be able to be recycled, that is to say that after crushing, the crushed particles are fed into an extruder, as defined above, where they are remixed by melting (recompounding) with the addition of at least one compound chosen from a semi-crystalline aliphatic polyamide, of recycled origin or not, of at least one modifier shock, a plasticizer, an additive and antistatic fillers (reformulation). The molten material emerges from the extruder in rods which are cooled and cut into granules.

A simply ground tube is therefore excluded from said used single-layer and/or multi-layer tube which has been intended for the transport of automotive fluid.

Grinding and recompounding without reformulation is also excluded.

The term “reformulation” therefore consists in adding other compounds chosen in particular from impact modifier, stabilizer, plasticizer and one or more other polyamides.

Optionally, the single-layer and/or multi-layer tube which has been intended for transporting automotive fluids undergoes a washing and/or cleaning step before grinding.

Optionally, the crushed tube undergoes a washing and/or cleaning step after crushing.

Optionally, the monolayer and/or multilayer tube which has been intended for the transport of automotive fluids undergoes a washing and/or cleaning step before grinding then is crushed and it then optionally undergoes, before recompounding, a washing step and/or cleaning after grinding.

The cleaning step can be carried out for example under vacuum.

In one embodiment, said layer (1) consists of a composition comprising:

at least 50% by weight, in particular from 50% to 97% by weight, of at least one semi-crystalline aliphatic polyamide noted C having an average number of carbon atoms per nitrogen atom noted C _C comprised of 6 to 18, advantageously from 8 to 12;

from 0 to 20% by weight of at least one plasticizer,

from 0 to 2% by weight of at least one additive, in particular a stabilizer, in particular an antioxidant

from 0 to 25% by weight of at least one semi-crystalline aliphatic polyamide noted B and having an average number of carbon atoms per nitrogen atom noted CB = Cc – 1, preferably CB = Cc – 2;

from 0 to 25% by weight of a semi-crystalline aliphatic polyamide noted A having an average number of carbon atoms per nitrogen atom noted CA = CB – 1, preferably CA = CB – 2;

from 0 to 45% by weight of at least one impact modifier, in particular from 3 to 45% by weight of at least one impact modifier, said impact modifier preferably being chosen from functionalized polyolefins, in particular functionalized with anhydride , or among the PEBAs

the sum of the constituents being equal to 100%.

In one embodiment, said composition of the layer (1) comprises:

at least 50% by weight, in particular from 50% to 99% by weight, in particular from 50% to 98% by weight, of at least one semi-crystalline aliphatic polyamide noted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 0 to 50%in weight at least one semi-crystalline aliphatic polyamide denoted B and having an average number of carbon atoms per nitrogen atom denoted C_B= Cc – 1, preferably C_B= Cc – 2;

from 0 to 50% by weight of a semi-crystalline aliphatic polyamide denoted A having an average number of carbon atoms per nitrogen atom denoted C _A = C _B – 1, preferably C _A = C _B – 2;

from 0 to 45% by weight of at least one impact modifier, in particular from 1 to 45% by weight of at least one impact modifier, in particular from 2 to 45% by weight of at least one impact modifier,

from 0 to 20% by weight of at least one plasticizer,

from 0 to 2% by weight of at least one additive,

the sum of the constituents being equal to 100%.

In another embodiment, said composition of the layer (1) consists of:

at least 50% by weight, in particular from 50% to 99% by weight, in particular from 50% to 98% by weight, of at least one semi-crystalline aliphatic polyamide noted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 0 to 25%in weight at least one semi-crystalline aliphatic polyamide denoted B and having an average number of carbon atoms per nitrogen atom denoted C_B= Cc – 1, preferably C_B= Cc – 2;

from 0 to 25% by weight of a semi-crystalline aliphatic polyamide noted A having an average number of carbon atoms per nitrogen atom noted C _A = C _B – 1, preferably C _A = C _B – 2;

from 0 to 45% by weight of at least one impact modifier, in particular from 1 to 45% by weight of at least one impact modifier, in particular from 2 to 45% by weight of at least one impact modifier,

from 0 to 20% of at least one plasticizer,

from 0 to 2% by weight of at least one additive,

the sum of the constituents being equal to 100%.

The polyamides rated A, B and C can be of recycled or non-recycled origin provided that the composition of the layer (1) consists of at least 50% recycled material.

Advantageously, the Tf of the majority aliphatic semi-crystalline polyamide of layer (1) is ≤225°C, in particular ≤200°C, as determined according to ISO 11357-3: 2013, at a heating rate of 20K/min .

In one embodiment, said composition of layer (1) is devoid of plasticizer and/or impact modifier and said recycled material comes from a shredded, recompounded and reformulated tube.

In another embodiment, said composition of the layer (1) comprises at least one compound chosen from plasticizer, an impact modifier and an additive, and said recycled material is chosen from a shredded tube, then recompounded and reformulated.

Advantageously, in these last two embodiments, said tube is a monolayer tube and/or a multilayer tube.

Advantageously, said at least one plasticizer is present from 2 to 20% by weight and/or said stabilizer is present from 0.2 to 2% by weight.

Advantageously, said at least one impact modifier is present from 1.5 to 45% by weight, preferably from 3 to 45% by weight.

In one embodiment, the fluid transported by said monolayer and/or multilayer tube is different from that of said monolayer tubular structure.

This means that if the single-layer and/or multi-layer tube has transported a fluid such as air, said single-layer tubular structure may be intended to transport gasoline or even if the single-layer and/or multi-layer tube has transported a fluid such as alcoholic gasoline, said single-layer tubular structure may be intended to transport diesel.

In another embodiment, the fluid transported by said monolayer and/or multilayer tube is the same as that of said monolayer tubular structure.

This means that if the single-layer and/or multi-layer tube has transported a fluid such as gasoline, said single-layer tubular structure may be intended to transport gasoline, provided that the gasoline of the single-layer and/or multi-layer tube and of said monolayer tubular structure is the same as, for example, alcoholic gasoline.

Advantageously, the recycled material comes from a single-layer tube consisting of a composition comprising only a PA11.

In one embodiment, said composition of the layer (1) comprises at least 60% by weight, in particular at least 70% by weight, in particular at least 80% by weight, in particular at least 90% by weight, more particularly at less than 95% recycled material.

In another embodiment, said composition of the layer (1) consists of 100% by weight of recycled material.

Recycled used single-layer or multi-layer pipe

In a first variant, said tube which was intended for the transport of automotive fluid is single-layer or multi-layer, ground, recompounded and reformulated and the composition of the layer (1) resulting from said recycling consists of:

at least 61% by weight, in particular from 96% to 99% by weight, in particular from 96% to 98% by weight, of at least one semi-crystalline aliphatic polyamide noted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 0 to 2% of at least one plasticizer,

from 0 to 2% by weight of at least one additive, in particular a stabilizer;

the sum of the constituents being equal to 100%.

Advantageously, in this first variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.

Advantageously in this first variant, said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, in this first variant, the semi-crystalline aliphatic polyamide noted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, said tube which was intended for the transport of fluid for automobiles is single-layered.

In a second variant, said tube which was intended for the transport of automotive fluid is single-layer or multi-layer, ground, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of:

at least 58.5% by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 6 to 14% of at least one plasticizer, in particular from 6 to 8%;

from 0.5 to 1.5% by weight of at least one additive, in particular a stabilizer;

the sum of the constituents being equal to 100%.

Advantageously, in this second variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.

Advantageously in this second variant, said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, in this second variant, the semi-crystalline aliphatic polyamide noted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, said tube which was intended for the transport of fluid for automobiles is single-layered.

In a third variant, said tube which was intended for the transport of automotive fluid is single-layer or multi-layer, ground, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of:

at least 58% by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 6 to 14% of at least one plasticizer, in particular from 6 to 8%;

from 1 to 2% by weight of at least one additive, in particular a stabilizer and a catalyst;

the sum of the constituents being equal to 100%.

Advantageously, in this third variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.

Advantageously in this third variant, said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, in this third variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, said tube which was intended for the transport of fluid for automobiles is single-layered.

Advantageously, the composition is degassed during the compounding, even more advantageously the degassing is located just after the melting zone, and before the plasticizer introduction zone such as BBSA or the like.

In a fourth variant, said tube which was intended for the transport of automotive fluid is single-layer or multi-layer, ground, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of:

at least 50% by weight, in particular from 50% to 99% by weight, in particular from 50% to 98% by weight, of at least one semi-crystalline aliphatic polyamide noted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 0 to 25%in weight at least one semi-crystalline aliphatic polyamide denoted B and having an average number of carbon atoms per nitrogen atom denoted C_B= Cc – 1, preferably C_B= Cc – 2;

from 0 to 25% by weight of a semi-crystalline aliphatic polyamide noted A having an average number of carbon atoms per nitrogen atom noted C _A = C _B – 1, preferably C _A = C _B – 2;

from 0 to 2% of at least one plasticizer,

from 0 to 2% by weight of at least one additive,

the sum of the constituents being equal to 100%.

Advantageously, in this fourth variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.

Advantageously in this fourth variant, said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, in this fourth variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, said tube which was intended for the transport of fluid for automobiles is single-layered.

In a fifth variant, said tube which was intended for the transport of automotive fluid is single-layer or multi-layer, ground, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of:

at least 55% by weight, in particular from 55% to 99% by weight, in particular from 55% to 98% by weight, of at least one semi-crystalline aliphatic polyamide noted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 0 to 45% by weight of at least one impact modifier, in particular from 1 to 45% by weight of at least one impact modifier, in particular from 2 to 45% by weight of at least one impact modifier,

the sum of the constituents being equal to 100%.

Advantageously, in this fifth variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.

Advantageously in this fifth variant, said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, in this fifth variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, said tube which was intended for the transport of fluid for automobiles is single-layered.

In a sixth variant, said tube which was intended for the transport of automotive fluid is single-layer or multi-layer, ground, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of:

at least 50% by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 0 to 43.5% by weight of at least one impact modifier, in particular from 1 to 43.5% by weight of at least one impact modifier, in particular from 2 to 43.5% by weight of at least an impact modifier,

from 6 to 14% of at least one plasticizer, in particular from 6 to 8%;

from 0.5 to 1.5% by weight of at least one additive, in particular a stabilizer;

the sum of the constituents being equal to 100%.

Advantageously, in this sixth variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.

Advantageously in this sixth variant, said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, in this sixth variant, the semi-crystalline aliphatic polyamide noted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, said tube which was intended for the transport of fluid for automobiles is single-layered.

In a seventh variant, said tube which was intended for the transport of automotive fluid is single-layer or multi-layer, ground, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of:

at least 50% by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 0 to 43% by weight of at least one impact modifier, in particular from 1 to 43% by weight of at least one impact modifier, in particular from 2 to 38% by weight of at least one impact modifier,

from 6 to 14% of at least one plasticizer, in particular from 6 to 8%;

from 1 to 2% by weight of at least one additive, in particular a stabilizer and a catalyst;

the sum of the constituents being equal to 100%.

Advantageously, in this seventh variant, the semi-crystalline aliphatic polyamide noted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.

Advantageously in this seventh variant, said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, in this seventh variant, the semi-crystalline aliphatic polyamide noted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, said tube which was intended for the transport of fluid for automobiles is single-layered.

In an eighth variant, said tube which was intended for the transport of automotive fluid is single-layer or multi-layer, ground, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of:

at least 50% by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 0 to 25%in weight at least one semi-crystalline aliphatic polyamide denoted B and having an average number of carbon atoms per nitrogen atom denoted C_B= Cc – 1, preferably C_B= Cc – 2;

from 0 to 25% by weight of a semi-crystalline aliphatic polyamide noted A having an average number of carbon atoms per nitrogen atom noted C _A = C _B – 1, preferably C _A = C _B – 2;

from 0 to 43% by weight of at least one impact modifier, in particular from 1 to 43% by weight of at least one impact modifier, in particular from 2 to 38% by weight of at least one impact modifier,

from 0 to 20% of at least one plasticizer,

from 0 to 2% by weight of at least one additive,

the sum of the constituents being equal to 100%.

Advantageously, in this eighth variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.

Advantageously in this eighth variant, said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, in this eighth variant, the semi-crystalline aliphatic polyamide noted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, said tube which was intended for the transport of fluid for automobiles is single-layered.

In a ninth variant, said tube which was intended for the transport of automotive fluid is single-layer or multi-layer, ground, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of:

at least 50% by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 0 to 25%in weight at least one semi-crystalline aliphatic polyamide denoted B and having an average number of carbon atoms per nitrogen atom denoted C_B= Cc – 1, preferably C_B= Cc – 2;

from 0 to 25% by weight of a semi-crystalline aliphatic polyamide noted A having an average number of carbon atoms per nitrogen atom noted C _A = C _B – 1, preferably C _A = C _B – 2;

from 1 to 43% by weight of at least one impact modifier, in particular from 2 to 38% by weight of at least one impact modifier,

from 0 to 20% of at least one plasticizer,

from 0 to 2% by weight of at least one additive,

the sum of the constituents being equal to 100%.

Advantageously, in this ninth variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.

Advantageously in this ninth variant, said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, in this ninth variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, said tube which was intended for the transport of fluid for automobiles is single-layered.

In a tenth variant, said tube which was intended for the transport of automotive fluid is single-layer or multi-layer, ground, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of:

at least 50% by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted C _C comprised from 6 to 18, advantageously from 8 to 12;

from 0 to 25%in weight at least one semi-crystalline aliphatic polyamide denoted B and having an average number of carbon atoms per nitrogen atom denoted C_B= Cc – 1, preferably C_B= Cc – 2;

from 0 to 25% by weight of a semi-crystalline aliphatic polyamide noted A having an average number of carbon atoms per nitrogen atom noted C _A = C _B – 1, preferably C _A = C _B – 2;

from 1 to 43% by weight of at least one impact modifier, in particular from 2 to 38% by weight of at least one impact modifier,

from 0 to 20% of at least one plasticizer,

from 0.1 to 2% by weight of at least one additive, in particular a heat stabilizer

the sum of the constituents being equal to 100%.

Advantageously, in this tenth variant, the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.

Advantageously in this tenth variant, said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, in this tenth variant, the semi-crystalline aliphatic polyamide noted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

Advantageously, said tube which was intended for the transport of fluid for automobiles is single-layered.

Regarding the impact modifier

The impact modifier is advantageously made up of a polymer having a flexural modulus of less than 100 MPa measured according to standard ISO 178: 2010, determined at 23°C with relative humidity: RH50%, and of Tg of less than 0°C (measured according to standard 11357-2: 2013 at the inflection point of the DSC thermogram, at a heating rate of 20 K/min), in particular a polyolefin.

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

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

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

-the homopolymers or copolymers of propylene.

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

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

- copolymers of ethylene with at least one product chosen from salts or esters of unsaturated carboxylic acids such as alkyl (meth)acrylate (for example methyl acrylate), or vinyl esters of carboxylic acids saturated such as vinyl acetate (EVA), the proportion of comonomer possibly reaching 40% by weight.

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

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

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

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

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

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

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

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

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

The functionalized polyolefin (B1) can also be a co- or ter-polymer of at least the following units: (1) ethylene, (2) alkyl (meth)acrylate or saturated carboxylic acid vinyl ester and (3) anhydride such as maleic anhydride or (meth)acrylic acid or epoxy such as glycidyl (meth)acrylate.

By way of example of functionalized polyolefins of this last type, mention may be made of the following copolymers, in which the ethylene preferably represents at least 60% by weight and in which the ter monomer (the function) represents, for example, from 0.1 to 10% by weight of the copolymer:

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

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

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

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

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

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

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

The molecular weight, the MFI index, the density of these polyolefins can also vary to a large extent, which those skilled in the art will appreciate. MFI, short for Melt Flow Index, is the Melt Flow Index. It is measured according to the ASTM 1238 standard.

Advantageously, the non-functionalized polyolefins (B2) are chosen from polypropylene homopolymers or copolymers and any homopolymer of ethylene or copolymer of ethylene and a comonomer of the higher alpha olefinic type such as butene, hexene, octene or 4-methyl 1-pentene. Mention may be made, for example, of PP, high-density PE, medium-density PE, linear low-density PE, low-density PE, very low-density PE. These polyethylenes are known to those skilled in the art as being produced according to a “radical” process, according to a “Ziegler” type catalysis or, more recently, according to a so-called “metallocene” catalysis.

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

Regarding additives

The additives optionally used in the compositions of the invention are the conventional additives used in polyamides well known to those skilled in the art and are described in particular in EP 2098580.

For example, they are chosen from a catalyst, an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a nucleating agent and a colorant, fibers reinforcement, a wax and mixtures thereof.

The term “catalyst” designates a polycondensation catalyst such as an inorganic or organic acid.

Advantageously, the proportion by weight of catalyst is between about 50 ppm to about 5000 ppm, in particular from about 100 to about 3000 ppm relative to the total weight of the composition.

Advantageously, the catalyst is chosen from phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof.

By way of example, the stabilizer can be a UV stabilizer, an organic stabilizer or more generally a combination of organic stabilizers, such as a phenol-type antioxidant (for example of the type of that of irganox® 245 or 1098 or 1010 of the company Ciba-BASF), a phosphite-type antioxidant (for example irgafos® 126 and irgafos® 168 from the company Ciba-BASF) and even possibly other stabilizers such as a HALS, which means Hindered Amine Light Stabilizer or light stabilizer of the hindered amine type (for example Tinuvin® 770 from the company Ciba-BASF), an anti-UV (for example Tinuvin® 312 from the company Ciba) or a phosphorus-based stabilizer. It is also possible to use antioxidants of the amine type such as Naugard® 445 from the company Crompton or alternatively polyfunctional stabilizers such as Nylostab® S-EED from the company Clariant.

This stabilizer can also be an inorganic stabilizer, such as a copper-based stabilizer. By way of example of such inorganic stabilizers, mention may be made of copper halides and acetates. Incidentally, one can possibly consider other metals such as silver, but these are known to be less effective. These copper-based compounds are typically associated with alkali metal halides, particularly potassium.

Regarding the plasticizer

The plasticizers are, by way of example, the plasticizers are chosen from benzene sulfonamide derivatives, such as n-butyl benzene sulfonamide (BBSA); ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide; hydroxybenzoic acid esters, such as ethyl-2-hexyl parahydroxybenzoate and decyl-2-hexyl parahydroxybenzoate; tetrahydrofurfuryl alcohol esters or ethers, such as oligoethyleneoxytetrahydrofurfuryl alcohol; and esters of citric acid or hydroxy-malonic acid, such as oligoethyleneoxy malonate.

It would not be departing from the scope of the invention to use a mixture of plasticizers.

The additives when they are present in the composition are advantageously present from 1 to 20% by weight, in particular from 5 to 15% by weight, in particular from 5 to 12% by weight.

With regard to antistatic charges

The antistatic fillers are for example chosen from carbon black, graphite, carbon fibers, carbon nanotubes, in particular carbon black and carbon nanotubes.

Regarding the structure

All the embodiments of the layer (1) described above in the paragraph "concerning the layer (1)" can be used for the structure detailed in this part.

Advantageously, said layer (1) is the layer in contact with the transported fluid.

Advantageously, the recycled material comes from a single-layer tube consisting of a composition comprising only a PA11, in particular the composition of layer (1) consists of 100% recycled material.

In one embodiment of the single-layer tubular structure, said composition of said layer (1) is devoid of polyamides denoted A and B.

In another embodiment of the single-layer tubular structure, said composition of said layer (1) comprises polyamides chosen from those denoted A, B and a mixture thereof.

Advantageously, in these last two embodiments, the layer (1) comes from a monolayer recycled tube.

Advantageously, in these last two embodiments, the layer (1) comes from a single-layer recycled tube and said composition of said layer (1) comprises at least one impact modifier.

Advantageously, in these last two embodiments, the layer (1) comes from a multilayer recycled tube.

Advantageously, in these two embodiments, the layer (1) comes from a multilayer recycled tube and said composition of said layer (1) comprises at least one impact modifier.

In one embodiment, said single-layer tubular is intended for the transport of fluids chosen from a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.

According to another aspect, the present invention relates to a process for manufacturing a single-layer tubular structure as defined above, comprising a grinding step and at least one recompounding step with reformulation of at least one single-layer tube and/or multilayer having been intended for the transport of automotive fluids.

In u embodiment, said reformulation consists of the addition of at least one impact modifier and / or at least one plasticizer and / or at least one stabilizer and / or at least one semi-aliphatic polyamide crystalline material rated B and/or of at least one semi-crystalline aliphatic polyamide rated A during the recompounding.

In one embodiment, said at least one step of recompounding with reformulation is carried out under weak degassing.

In another embodiment, said at least one step of recompounding with reformulation is carried out under strong degassing.

In yet another embodiment, a step of extruding the ground and recompounded tube with reformulation is carried out to obtain the tubular structure.

According to yet another aspect, the present invention relates to the use of at least one monolayer and/or multilayer tube having been intended for the transport of fluids for motor vehicles as defined above, for the preparation of a monolayer tubular structure intended for transporting automotive fluids, in particular air, oil, water, a urea solution, a glycol-based coolant, or a fuel such as gasoline, in in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen as defined above.

EXAMPLES:

The following resins were used in the various compositions of the invention:

PA11: Polyamide 11 of Mn (molecular mass in number) 29000. The melting temperature is 190° C., its enthalpy of fusion is 56 kJ/m2. The composition of this PA11 includes 0.25% (+/-0.05%) of H3PO4.

PA12: Polyamide 12 of Mn (molecular weight in number) 35000. The melting temperature is 178°C, its enthalpy of fusion is 54kJ/m2

PA1012: Polyamide 1012 of Mn (molecular weight in number) 27000. The melting temperature is 190°C, its enthalpy of fusion is 57kJ/m2

The melting temperature and enthalpy of melting were determined according to ISO 11357-3:2013.

The following additives, plasticizers and impact modifiers were used in the compositions of the invention:

stabilizer: stabilizer consisting of 80% Lowinox 44B25 phenol from the Great Lakes company, 20% Irgafos 168 phosphite from the Ciba company

BBSA: plasticizer BBSA (benzyl butyl sulfonamide),

Imod = generically designates an impact modifier of the polyolefin or other type such as, among others, PEBA (polyether-block-amide), core-shell, silicones, etc.

Imod1: denotes an EPR functionalized with an anhydride function reactive group (at 0.5-1% by mass), of MFI 9 (at 230° C., under) 10 kg, of the Exxellor VA1801 type from the company Exxon.

Imod2: impact modifier of the ethylene/ethyl acrylate/anhydride type in a mass ratio of 68.5/30/1.5 and MFI 6 at 190° C. under 2.16 kg.

The following compositions were used to manufacture the tubes according to the invention:

Throughout the description all percentages are given by weight.

In the case of the compositions called “recy”, “recy2” and “recy3” used for the layer (1) of the tubes of the invention or the counterexample tubes, protocols for simulating an aged tube were used:

Protocol A: The tube is (artificially) aged according to an easily reproducible model protocol which consists of placing it in air (in the presence of oxygen) at 150°C for 96 hours (4 days), in order to thermo-oxidize it . This model aging is representative of the average thermo-oxidation that the tubes undergo in 10 years of service in a vehicle next to a hot engine.

The results obtained on impact, aging, flexural modulus, adhesion and elongation show that protocol A is representative of a reground gasoline tube.

Special protocols used during the (re)compounding of the aged tube.

After aging, the crushed tube can in certain cases be recompounded according to two protocols:

Protocol B: the reground tube is recompounded on a Coperion/Werner 40 mm twin-screw extruder, 70 kgh, 300 rpm, 270° C. set point, with a degassing of −100 mmHg.

Protocol B2: the reground tube is recompounded on a Coperion/Werner 40mm twin-screw extruder, 70kgh, 300rpm, 270°C setpoint, with strong degassing of -660mmHg.

The different compositions used for the preparation of the tubes of the invention are as follows (percentages by weight):

PA11PL = PA11 + 7% BBSA + 1% stabilizer

PA12PL = PA12 + 12% BBSA + 1% stabilizer

PA11NX3 = PA11 + imod2 10% + PA610 5% + PA6 5% + BBSA 4% + stabilizer 1%

PA11PL-recy = tube of PA11PL aged according to protocol A, reground, to be then recycled.

PA11PL-recyNX3 = PA11PL tube aged according to protocol A, reground, recompounded according to protocol B, with during this recompounding addition of imod2 10%, PA610 5%, PA6 5%, BBSA 4% and stab 1%, to be subsequently recycled.

PA11PL-recy3 = tube of PA11PL aged according to protocol A, reground, recompounded according to protocol B2, recompounding with strong degassing, with during this recompounding addition of 6% of imod3 and 5% of BBSA, to be then recycled.

PA11NX3-recy2 = PA11NX3 tube aged according to protocol A, reground, recompounded according to protocol B2, recompounded with strong degassing, with during this recompounding addition of 3% BBSA and 0.5% stabilizer, to be then recycled.

PA12PL-recy = tube of PA12PL aged according to protocol A, reground, to be then recycled.

PA1012PL4 = PA1012 + 12% BBSA + 1% stabilizer

PA1012-recy = tube of PA1012PL4 aged according to protocol A, reground, to be then recycled

PA12HIPHL= PA12 + 6% imod1 + 10%BBSA + 1%stabilizer

PA12HIP-recy3 = PA12HIPHL tube aged according to protocol A, reground, recompounded according to protocol B, with during this recompounding addition of 6%imod1, 9%BBSA and 1% stab, to be then recycled;

These compositions are manufactured by conventional compounding in a co-rotating twin-screw extruder of the Coperion 40 type, at 300 rpm, at 270° C. (or at 300° C. when the ingredients have a melting point above 260° C.).

Monolayer tubes of the invention:

the tubes are 8*1mm in size

Preparation of single-layer structures (tubes):

Monolayer structures are made by extrusion. We use an industrial Maillefer extrusion line.

This line includes a single-screw extrusion extruder equipped with a screw with a screw profile suitable for polyamides. In addition, the extrusion line includes:

a die-punch assembly, located at the end of the extrusion head; the internal diameter of the die and the external diameter of the punch are chosen according to the structure to be made and the materials of which it is made, as well as the dimensions of the tube and the line speed;

a vacuum tank with an adjustable vacuum level. In this tank circulates water maintained at 20°C in general, in which is immersed a gauge allowing to conform the tube in its final dimensions. The diameter of the gauge is adapted to the dimensions of the tube to be produced, typically from 8.5 to 10 mm for a tube with an external diameter of 8 mm and a thickness of 1 mm;

a cooling tank in which water is kept at around 20°C, allowing the tube to be cooled along the route from the head to the draw bench;

a diameter gauge;

a draw bench.

Before the tests, in order to ensure the best tube properties and good extrusion quality, it is checked that the extruded materials have a residual moisture content before extrusion of less than 0.08%. Otherwise, an additional stage of drying the material is carried out before the tests, generally in a vacuum dryer, for 1 night at 80°C.

The tubes, which meet the characteristics described in this patent application, were sampled, after stabilization of the extrusion parameters, the dimensions of the targeted tubes no longer changing over time. The diameter is controlled by a laser diameter gauge installed at the end of the line.

Line speed is typically 20m/min. It generally varies between 5 and 100m/min.

The screw speed of the extruders depends on the thickness and diameter of the tube as known to those skilled in the art.

In general, the temperatures of the extruders and the tools (head and connection) must be adjusted so as to be sufficiently higher than the melting temperature of the compositions under consideration, so that they remain in the molten state, thus avoiding they solidify and block the machine.

The single-layer tubes made by extrusion above were then evaluated on several criteria:

Shock: designates the shock type VW-40°C standard VW TL52435 2010

We note "++", a shock performance that can be described as "very good", which corresponds to <= 10% breakage.

We note "+", a shock performance that can be described as "good", which corresponds to <= 25% breakage and > 10% breakage

We note "-", a shock performance that can be described as "fairly bad", which corresponds to <= 75% breakage and > 25%

We note "--", a shock performance that can be described as "very poor", which corresponds to > 75%

Aging (Viell.): This is the durability, in other words it designates the resistance of the tube to oxidative aging in hot air. The tube is left to age in air at 150°C, then it is shocked with a shock according to the DIN 73378 standard, this shock being carried out at -40°C, the half-life (in hours) which corresponds at the end of which 50% of the tubes tested break. A qualitative comment accompanies this value.

We note "++", a durability that can be described as "very good", which corresponds to >= 200h of half-life.

We note "+", a durability (resistance to thermo-oxidative aging) that can be described as "good", which corresponds to >= 100h of half-life (and <200h)

We note "+-", a durability (resistance to thermo-oxidative aging) that can be described as "acceptable", which corresponds to >= 50h of half-life (and <100h)

We note "-", a durability (resistance to thermo-oxidative aging) that can be described as "poor", which corresponds to <50h

In the case where a half-life figure is given to show nuances, this figure is rounded off by 25h increments, to take account of significant figures, linked to the precision of the evaluation.

Table 1 presents the PA11 tubes (examples and counter-examples) and table 2 presents the PA12 tubes (example and counter-example)

Example Structure Shock Old. Ex1 Monolayer PA11PL-recyNX3 ++ + Ex2 Monolayer PA11PL-recy3 ++ + Ex3 Monolayer PA11NX3-recy2 ++ +- against
examples cx2 monolayer PA11PL-recy + -

NT: Not tested

Example Structure Shock Old. Ex4 Monolayer PA12HIP-recy3 + - against
examples cx1 Monolayer PA12PL-recy -- -

Claims (20)

Monolayer tubular structure intended for the transport of automotive fluids, in particular air, oil, water, a urea solution, a glycol-based coolant, or a fuel such as gasoline. gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, consisting of a layer (1) consisting of a composition mainly comprising at least a semi-crystalline aliphatic polyamide, said composition consisting of at least 50% of recycled material originating from at least one single-layer and/or multi-layer tube having been intended for the transport of automotive fluids, in particular as defined above , said tube consisting of a composition which mainly comprises at least one polyamide,
said at least one tube having undergone grinding and recompounding with reformulation to be able to be recycled,
simple single grinding or grinding and recompounding without reformulation being excluded. Monolayer tubular structure according to Claim 1, in which the said layer (1) consists of a composition comprising:
at least 50% by weight, in particular from 50% to 97% by weight, of at least one semi-crystalline aliphatic polyamide noted C having an average number of carbon atoms per nitrogen atom noted C _C comprised of 6 to 18, advantageously from 8 to 12;
from 0 to 20% by weight of at least one plasticizer,
from 0 to 2% by weight of at least one additive, in particular of a stabilizer, in particular of an antioxidant
from 0 to 25% by weight of at least one semi-crystalline aliphatic polyamide noted B and having an average number of carbon atoms per nitrogen atom noted CB = Cc – 1, preferably CB = Cc – 2;
from 0 to 25% by weight of a semi-crystalline aliphatic polyamide noted A having an average number of carbon atoms per nitrogen atom noted CA = CB – 1, preferably CA = CB – 2;
from 0 to 45% by weight of at least one impact modifier, in particular from 3 to 45% by weight of at least one impact modifier, said impact modifier preferably being chosen from functionalized polyolefins, in particular functionalized with anhydride , or among the PEBAs
the sum of the constituents being equal to 100%. Monolayer tubular structure according to Claim 2, in which the said composition of the layer (1) is devoid of plasticizer and/or impact modifier. Monolayer tubular structure according to Claim 2, in which the said composition of the layer (1) comprises at least one compound chosen from plasticizer, an impact modifier and an additive. Monolayer tubular structure according to claim 4, wherein said at least one plasticizer is present from 2 to 20% by weight and/or said stabilizer is present from 0.2 to 2% by weight. Monolayer tubular structure according to Claim 4 or 5, in which the said at least one impact modifier is present from 1.5 to 45% by weight, preferably from 3 to 45% by weight. Monolayer tubular structure according to Claim 6, in which the said at least one semi-crystalline aliphatic polyamide denoted B is present. Monolayer tubular structure according to Claim 6 or 7, in which the said at least one semi-crystalline aliphatic polyamide denoted A is present. Monolayer tubular structure according to one of claims 1 to 8, in which the fluid transported by said at least one monolayer and/or multilayer tube is the same as that of said monolayer tubular structure. Monolayer tubular structure according to one of Claims 1 to 8, in which the fluid transported by said at least one monolayer and/or multilayer tube is different from that of said monolayer tubular structure. Monolayer tubular structure according to one of Claims 1 to 10, in which the said at least one tube is a monolayer recycled tube. Monolayer tubular structure according to one of Claims 1 to 10, in which the said at least one tube is a multilayer recycled tube Monolayer tubular structure according to one of Claims 1 to 12, in which the Tf of the predominant aliphatic semi-crystalline polyamide of the layer (1) is ≤225°C, in particular ≤ 200°C as determined by DSC according to the standard ISO 11357-3:2013, at a heating rate of 20K/min. Monolayer tubular structure according to one of Claims 1 to 13, in which the predominant aliphatic semi-crystalline polyamide of layer (1) has an enthalpy of crystallization ≥ 25 J/g, preferentially ≥ 40 J/g, in particular ≥ 45 J/g as determined by DSC according to ISO 11357-3:2013, at a heating rate of 20K/min. Process for the manufacture of a single-layer tubular structure as defined in claim 1, comprising a step of grinding and at least one step of recompounding with reformulation of at least one single-layer and/or multi-layer tube having been intended for the transport of fluids for automobile. Process according to Claim 12, in which the said reformulation consists of the addition of at least one impact modifier and/or of at least one plasticizer and/or of at least one stabilizer and/or of at least one aliphatic polyamide semi-crystalline rated B and/or of at least one semi-crystalline aliphatic polyamide rated A during the recompounding. Process according to Claim 15 or 16, in which at least one step of recompounding with reformulation is carried out under weak degassing. Process according to Claim 15 or 16, in which at least one step of recompounding with reformulation is carried out under strong degassing. Method according to one of Claims 15 to 18, in which a step of extruding the crushed and recompounded tube with reformulation is carried out to obtain the tubular structure. Use of at least one single-layer and/or multi-layer tube having been intended for the transport of fluids for motor vehicles as defined in claim 1, for the preparation of a single-layer tubular structure intended for the transport of fluids for motor vehicles, in particular air, oil, water, urea solution, glycol-based coolant, or a fuel such as gasoline, especially alcoholic gasoline, bio- petrol or diesel, in particular bio-diesel, or hydrogen as defined in claim 1.