Composition containing thermoplastic elastomer and crosslinked rubber powder

Abstract

The present invention relates to a composition comprising, relative to the total weight of the composition, the following components: at least one thermoplastic elastomer (TPE), preferably an elastomeric thermoplastic copolymer, in an amount of 20% to 90% by weight, preferably 40% to 70% by weight, 0.08m 2 / g and 100m 2 / g, preferably between 0.1 and 80m 2 / g, and more preferentially between 0.1 and 50m 2 At least one crosslinked rubber powder having a specific surface area of ​​between 10% by weight and 80% by weight, preferably 30% by weight and 60% by weight, - 0 to 5% of additives, preferably 0.1% to 4%, in particular 1% to 2%; - 0-40%, preferably 5-20%, in particular 10-15% of a compatibilizer.

Description

[Technical field]

[0001] The present invention relates to a composition based on thermoplastic elastomers and crosslinked rubber powder, in particular obtained from the grinding of used tires, and to a process for its manufacture. The present invention also relates to articles consisting of or containing elements of such compositions, such as shoe soles, their manufacture and their recycling. The present invention also relates to the granules, filaments or powder obtained by this recycling process, and to the articles prepared therefrom. [Background technology]

[0002] Thermoplastic elastomers (TPEs) are used in particular in the field of sports equipment such as shoe soles and sole components, gloves, rackets, golf balls, personal protective equipment for sports practice (jackets, internal parts of helmets, shells, etc.), etc. Such applications require materials with a set of specific physical properties, such as good resilience, low residual tensile strain, the ability to withstand repeated impacts and return to their original shape.

[0003] Additionally, there is an increasing need to use recycled materials such as used tires.

[0004] WO 17 / 021164 describes a composition comprising rubber powder, a thermoplastic polyurethane obtained from a polyisocyanate and a polyol, and a polysiloxane. This composition can be used for shock absorption, especially in shoe soles.

[0005] There is a real need to provide a composition that has good springback and low density, while at the same time having good wear resistance, good anti-slip properties, and good tensile strength. Summary of the Invention

[0006] The present invention relates first to a composition comprising the following components based on the total weight of the composition: at least one thermoplastic elastomer (TPE), preferably an elastomeric thermoplastic copolymer, in an amount of 20% to 90% by weight, preferably 40% to 70% by weight, 0.08m 2 / g and 100m 2 / g, preferably between 0.1 and 80m 2 / g, more preferably between 0.1 and 50m 2 At least one crosslinked rubber powder having a specific surface area of ​​between 10% by weight and 80% by weight, preferably 30% by weight and 60% by weight, - 0 to 5% of additives, preferably 0.1% to 4%, in particular 1% to 2%; - 0-40%, preferably 5-20%, in particular 10-15% of a compatibilizer.

[0007] In a particular embodiment of the composition according to the invention, - Crosslinked rubber powder is 0.08m 2 / g and 0.5m 2 / g, preferably between 0.1 and 0.3 m 2 / g, more preferably between 0.1 and 0.2 m 2 / g, the crosslinked rubber powder has an average diameter D50 between 2 μm and 500 μm, preferably between 50 μm and 300 μm, and more preferably between 60 μm and 200 μm; the diameter D90 of the crosslinked rubber powder is between 10 μm and 800 μm, preferably between 80 μm and 500 μm, and more preferably between 100 μm and 300 μm; the rubber of the crosslinked rubber powder is natural rubber, synthetic rubber or a mixture thereof; The rubber of the crosslinked rubber powder contains 10% by weight to 80% by weight, preferably 15% by weight to 70% by weight, of natural rubber; the natural rubber is cis-1,4-polyisoprene or trans-1,4-polyisoprene; the crosslinked rubber powder comprises styrene-butadiene rubber, preferably with a content of more than 5% by weight, more preferably with a content of more than 10% by weight, - Crosslinked rubber powder is obtained from used tires, - Crosslinked rubber powder is obtained by water jet cutting of tires; the crosslinked rubber powder contains 1% to 70%, preferably 5% to 50%, and more preferably 10% to 40% of carbon black and / or silica, the at least one TPE is selected from polyamide elastomers, thermoplastic polyurethanes, polyester elastomers, styrene-butadiene block copolymers, styrene-ethylene-butadiene block copolymers, and mixtures thereof, preferably selected from polyamide elastomers, thermoplastic polyurethanes, polyester elastomers, and mixtures thereof; the TPE comprises flexible polyether and / or polyester blocks, preferably polyether, more preferably PTMG, and / or rigid blocks selected from polyamide, polyurethane and polyester, the rigid block is a polyamide comprising at least one Z or XY type unit, Z is a lactam or amino acid containing 6 to 18 carbon atoms; X is a diamine containing 4 to 48 carbon atoms; Y is a diacid containing 6 to 48 carbon atoms; the rigid block is a polyamide comprising at least one Z or XY type unit, X is a diisocyanate, Y is a diol, The rigid block is a polyester containing at least one XY unit, X is a dicarboxylic acid, Y is a diol, The ratio of the flexible block to the rigid block is selected so that the tensile modulus according to ISO 527 is between 5 MPa and 800 MPa, preferably between 10 MPa and 300 MPa, more preferably between 20 MPa and 150 MPa, The TPE has a Shore hardness between 10D and 70D, preferably between 25D and 50D.

[0008] The present invention also relates to a method for preparing a composition according to the invention, said method comprising the steps of: Preferably in an extruder, o at least one thermoplastic elastomer, preferably a copolymer, in the molten state, at 20% to 90% by weight, preferably at 40% to 70% by weight, and o0.08m 2 / g~100m 2 / g, preferably 0.1 to 80 m 2 / g, more preferably 0.1 to 50 m 2 At least one crosslinked rubber powder having a specific surface area of ​​10% by weight to 80% by weight, preferably 30% by weight to 60% by weight, - 0 to 5% of additives, preferably 0.1% to 4%, in particular 1% to 2%; -0 to 40%, preferably 5 to 20%, in particular 10 to 15% and mixing the Optionally, forming the mixture into the form of granules, filaments or powder; and / or - Recovering the resulting composition. Includes.

[0009] The present invention also relates to an article consisting of or comprising at least one element consisting of or comprising a composition according to the invention.

[0010] The article is preferably selected from footwear components such as shoe soles, ski pole parts, racket and golf club handles, goalkeeper gloves, sporting goods parts such as treadmills, underwater equipment such as diving boots, masks and snorkel parts, eyeglass frame parts (sleeves, temples, nose pads), ski mask frames, vibration isolation parts for electronic devices and machines, external battery shells, automotive parts (seals, end caps), toys, watch bands, machine buttons, seals or conveyor belt components.

[0011] The present invention also relates to a method for producing an article according to the invention, said method comprising the steps of: - providing a composition according to the invention; - injection molding said composition; The present invention relates to a method comprising the steps of:

[0012] The present invention also relates to a method for recycling an article according to the invention, comprising the following successive steps: a) recovering, optionally after separation, at least a portion of said article made of a thermoplastic material comprising the composition of the present invention; b) grinding the thermoplastic material to obtain particles; c) melting the particles to obtain a molten mixture; d) optionally adding other ingredients to the molten mixture; e) optionally forming granules, filaments or powder from the molten mixture obtained at the end of step c) or step d); f) optionally forming the granules, filaments or powder; Includes.

[0013] The present invention also relates to the granules, filaments or powder obtained according to the recycling method according to the invention.

[0014] The invention also relates to an article consisting of or comprising at least one element prepared from said granules, filaments or powder.

[0015] The present invention makes it possible to meet the above needs. More specifically, a composition is provided that has good abrasion resistance, good anti-slip properties as measured by the coefficient of friction, and good tensile properties. The composition has good elastic recovery, high elongation at break, good adhesion to wet surfaces, and is recyclable due to its meltability.

[0016] This is achieved by using specific amounts of at least one thermoplastic elastomer (TPE), preferably an elastomeric thermoplastic copolymer, and at least one crosslinked rubber powder with a well-defined specific surface area. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The invention is explained in more detail and in a non-limiting manner in the following description.

[0018] Thus, according to a first aspect, the invention relates to a composition comprising, relative to the total weight of the composition: at least one thermoplastic elastomer (TPE), preferably an elastomeric thermoplastic copolymer, in an amount of 20% to 90% by weight, preferably 40% to 70% by weight, 0.08m 2 / g~100m 2 10% by weight to 80% by weight, preferably 30% by weight to 60% by weight, of at least one crosslinked rubber powder having a specific surface area of ​​100 / g; - 0 to 5% of additives, preferably 0.1% to 4%, in particular 1% to 2%; - 0-40%, preferably 5-20%, in particular 10-15% of a compatibilizer.

[0019] Crosslinked rubber powder The crosslinked rubber powder used in the composition of the present invention has a viscosity of 0.08 m 2 / g and 100m 2 The powder can be characterized by a specific surface area between 100 nm and 150 nm / g, which is measured by the BET method described in Shen et al., Constr. Build. Mater. 2009, 23(1), 304-310.

[0020] According to a preferred embodiment, the specific surface area of ​​the rubber powder is 0.08 m 2 / g and 100m 2 / g, especially 0.1m 2 / g and 80m 2 / g, most especially 0.1m 2 / g and 50m 2 / g, especially 0.1m 2 / g and 0.3m 2 / g, more preferably 0.1m 2 / g and 0.2m 2 / g. Preferably between 0.1m 2 / g and 0.18m 2 / g, especially 0.12m 2 / g and 0.16m 2 / g.

[0021] Preferably, the crosslinked rubber powder has a specific particle size, in particular a specific D50, D90 and / or D10 diameter, which characterizes the size distribution of the crosslinked rubber particles.

[0022] The crosslinked rubber powder preferably has a mean diameter D50 between 2 μm and 500 μm, preferably between 50 μm and 300 μm, more preferably between 60 μm and 200 μm.

[0023] The D90 diameter of the powder is in particular between 10 μm and 800 μm, preferably between 80 μm and 500 μm, and more preferably between 100 μm and 300 μm.

[0024] The diameter D10 of the powder is in particular between 1 μm and 300 μm, preferably between 5 μm and 200 μm, and more preferably between 10 μm and 100 μm.

[0025] The term "diameter" or "D" of a powder refers to the mass average diameter of the powder material as measured by the "Ro-tap Sieve Test" method using a machine such as the RX-94 Duo or RO-TAP Premium sold by WS. Tyler is equipped with sieves that comply with the standard ISO 3310-1:2016.

[0026] Different diameters are distinguished. More precisely, D50 denotes the mass mean diameter, i.e. the diameter at which less than 50% of the particles by mass are contained. D10 and D90 also denote the diameter at which less than 10% or 90% of the particles by mass are present, respectively.

[0027] As used herein, the term "crosslinked rubber" means a crosslinked elastomer.

[0028] The rubber of the crosslinked rubber crumb may be natural rubber, synthetic rubber or a mixture thereof.

[0029] The rubbers used in the manufacture of rubber powder may be virtually any type of sulfur vulcanized rubber compound and may be obtained from a variety of sources, including brominated butyl rubber, butyl rubber, polyisoprene rubber, polynorbornene rubber, ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), nitrile rubber, carboxylated nitrile rubber, polychloroprene rubber (neoprene rubber), polysulfide rubber, polyacrylic rubber, silicone rubber, chlorosulfonated polyethylene rubber, polybutadiene-containing rubber, styrene butadiene rubber, and the like, as well as various mixtures thereof.

[0030] The rubber of the crosslinked rubber powder may contain 0 to 50% by weight, preferably 5 to 40% by weight, of synthetic rubber or a mixture of synthetic rubbers.

[0031] The rubber of the crosslinked rubber powder may contain 10% to 80% by weight, and preferably 15% to 70% by weight, of natural rubber.

[0032] The natural rubber may in particular be chosen from cis-1,4-polyisoprene or trans-1,4-polyisoprene.

[0033] The rubber of the rubber powder may contain styrene-butadiene rubber, the content of which is preferably greater than 5% by weight, more preferably greater than 10% by weight.

[0034] Crosslinked rubber powder can be obtained from various sources, in particular from the recycling of industrial waste and finished post-consumer products. Such objects come from a wide range of sectors, such as: in the clothing sector, in particular shoe outsoles and boots; in the automotive sector, sealing parts such as gaskets, airbags, floor mats, anti-vibration supports and fittings; in the industrial sector, conveyor belts, belts, drinking water seals, O-rings, cables and pipes; in the consumer sector, window seals, mattress foams, golf balls, tennis balls, windsurfing suits, masks and flippers; in the construction sector, seismic bridges and columns, flexible tanks and profiles; in the hygiene and medical sector, gloves and baby bottle nipples.

[0035] The crosslinked rubber powder is characterized in that it is obtained from the recycling of used products. This may in particular include used tires, in particular tires at the end of their life and / or tires that have traveled at least 20 km. Recycled crosslinked rubber, in particular obtained from used tires, may contain more functionalities generated during the thermo-oxidation reaction than rubber that has never been used. These functional groups are in particular carbonyl, hydroxyl or sulfenic acid, such as phenylhydrazones, ketones, etc., and in free form carbonyl and sulfenic acid functional groups.

[0036] Without being bound to any particular theory, these polar functionalities may improve the interaction between the thermoplastic TPE-based matrix and the crosslinked rubber powder particles, enhancing the physical properties of the composite.

[0037] One example of a source of crosslinked rubber powder obtained from used tires is the rubber compound recovered during grinding of the vehicle tire tread during a regrooving procedure, however, as noted above, the rubber compound may be obtained from a variety of sources, such as whole tires, tire sidewalls, tire innerliners, tire carcasses, power transmission belts, conveyor belts, pipes, and various other rubber products.

[0038] Thus, the crosslinked rubber powder used according to the present invention is typically a powder of a mixture of natural and synthetic rubbers, such as polyisoprene synthetic rubber, polybutadiene rubber, styrene butadiene rubber, etc. However, the crosslinked rubber powder used according to the present invention may be a mixture of two or more of these rubbers, or may consist of a single type of rubber. For example, the crosslinked rubber powder may consist only of natural rubber, synthetic polyisoprene rubber, styrene butadiene rubber, a mixture of natural rubber and polybutadiene rubber, or a mixture of natural rubber and styrene butadiene rubber.

[0039] Crosslinked rubber powder can be prepared according to various methods. As an example, rubber powder can be obtained by a grinding process. There are various grinding processes, such as mechanical grinding at room temperature, cryogenic grinding, grinding using water jets, and powder pulverization. Water jet grinding (also called water jet cutting) is particularly suitable for used tires.

[0040] The crosslinked rubber powder may contain 1% to 70%, preferably 5% to 50%, and more preferably 10% to 40% of carbon black and / or silica.

[0041] In one embodiment, the crosslinked rubber powder comprises carbon black and silica, the silica content being advantageously about twice the carbon black content, and most advantageously about five times, expressed as a weight content relative to the total weight of the composition.

[0042] Furthermore, the crosslinked rubber powder may contain less than 10%, advantageously less than 5%, and very advantageously less than 1% of fibrous material.

[0043] Preferably, the composition is free of glass fibers.

[0044] Furthermore, the crosslinked rubber powder may contain 0.05% to 5% by weight, preferably 0.1% to 2.5% by weight, of zinc oxide.

[0045] Thermoplastic Elastomers (TPE) / Elastomer Thermoplastic Copolymers The term "thermoplastic elastomer" or "TPE" refers to polymers that combine the elastic properties of elastomers with thermoplastic properties, i.e. they melt and harden reversibly under the action of heat. These thermoplastic elastomers are in particular mechanical polymer mixtures, i.e. "polymer-polymer" mixtures, usually mixtures of thermoplastic polymers and elastomers, or they may be thermoplastic elastomer copolymers.

[0046] The term "thermoplastic elastomer copolymer" refers to a polymer that contains flexible and rigid segments, for example in the form of a block copolymer, where the rigid segments are generally semi-crystalline or have a high glass transition temperature and melt or soften with increasing temperature. Above the melting point or glass transition temperature of the rigid segment domains, the material can be used with conventional thermoplastic polymer processing techniques. Below the melting point of the rigid segment domains, the thermoplastic elastomer has elastic properties approaching those of crosslinked elastomers.

[0047] The flexible and rigid blocks are covalently linked in various elastomers by functional groups selected from amides, esters, urethanes, and ureas, among others.

[0048] According to a particular embodiment, the at least one TPE copolymer is selected from polyamide elastomers, thermoplastic polyurethanes, polyester elastomers, styrene-butadiene block copolymers and styrene-ethylene-butadiene block copolymers, preferably polyether block amides (PEBA), thermoplastic polyurethanes (TPU) and polyester elastomers.

[0049] According to another embodiment, the TPE copolymer advantageously comprises rigid blocks chosen from polyamides, polyurethanes and polyesters.

[0050] According to a particular embodiment, the ratio of the flexible block to the rigid block is selected so that the tensile modulus according to ISO 527 is between 5 MPa and 800 MPa, preferably between 10 MPa and 300 MPa, and more preferably between 20 MPa and 150 MPa.

[0051] According to a particular embodiment, the TPE copolymer has a Shore hardness between 10D and 70D, in particular between 25D and 45D.

[0052] According to a particular embodiment, the composition comprises a mixture of TPE copolymers, in particular a mixture of PEBA, TPU and / or thermoplastic polyesters.

[0053] According to a particular embodiment, the mixture is in particular a TPE copolymer alloy. The term "alloy" means a homogeneous mixture (visible to the naked eye). In one embodiment, the various TPE copolymers are bonded via one or more covalent bonds. The groups capable of linking the two TPE copolymers are selected from urethanes, ureas, amides, and esters.

[0054] As an example, in the context of a TPU-PEBA alloy, the two copolymers TPU and PEBA may be bonded via one or more covalent bonds.

[0055] In certain embodiments, at least a portion of the polyamide block-polyether block copolymer is covalently bonded to at least a portion of the thermoplastic polyurethane by urethane functional groups, and preferably no more than 10 wt %, more preferably no more than 5 wt %, of the polyamide block-polyether block copolymer is covalently bonded to at least a portion of the thermoplastic polyurethane by urethane functional groups.

[0056] [PEBA] The copolymer is in particular a thermoplastic polyamide, in particular a PEBA copolymer.

[0057] PEBA is produced by polycondensation of a polyamide block (hard or hard block) having a reactive end and a polyether block (soft or soft block) having a reactive end, for example, among others: 1) a polyamide block having a diamine chain end and a polyoxyalkylene block having a dicarboxyl chain end; 2) A polyamide block having a polyether diol at the dicarboxyl chain end (α,ω-dihydroxylated aliphatic polyoxyalkylene block) where the resulting product is, in this particular case, a polyetheresteramide.

[0058] Polyamide blocks with dicarboxyl chain ends result, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid. Polyamide blocks with diamine chain ends result, for example, from the condensation of polyamide precursors in the presence of a chain-limiting diamine.

[0059] Three types of polyamide blocks can be advantageously used.

[0060] According to a first type, the polyamide blocks result from the condensation of dicarboxylic acids, in particular those containing from 4 to 36 carbon atoms, preferably those containing from 4 to 20 carbon atoms and more preferably those containing from 6 to 18 carbon atoms, with aliphatic or aromatic diamines, in particular those containing from 2 to 20 carbon atoms and preferably those containing from 6 to 14 carbon atoms.

[0061] Examples of dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, terephthalic acid, isophthalic acid, and dimerized fatty acids.

[0062] Examples of diamines include tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, bis(4-aminocyclohexyl)methane (BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM), isomers of 2,2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP), paraaminodicyclohexylmethane (PACM), isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN), and piperazine (Pip).

[0063] Advantageously, the polyamide blocks PA 4.12, PA 4.14, PA 4.18, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA 9.12, PA 10.10, PA 10.12, PA 10.14 and PA 10.18 are used. In the notation PA XY, X represents the number of carbon atoms originating from the diamine residue and Y represents the number of carbon atoms originating from the diacid residue as is conventional.

[0064] According to a second type, the polyamide blocks result from the condensation of one or more α,ω-aminocarboxylic acids and / or one or more lactams containing 6 to 12 carbon atoms in the presence of dicarboxylic acids or diamines containing 4 to 18 carbon atoms. Examples of lactams include caprolactam, enantholactam, lauryllactam, etc. Examples of α,ω-aminocarboxylic acids include aminocaproic acid, 7-aminoheptanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.

[0065] Advantageously, the second type of polyamide block is a PA 10 (polydecane amide), PA 11 (polyundecane amide), PA 12 (polydodecanamide) or PA 6 (polycaprolactam) block. In the notation PA X, X represents the number of carbon atoms originating from an amino acid residue.

[0066] According to a third type, the polyamide blocks result from the condensation of at least one α,ω-aminocarboxylic acid (or lactam), at least one diamine and at least one dicarboxylic acid.

[0067] In this case, the polyamide PA block is - a linear aliphatic or aromatic diamine containing X carbon atoms, a dicarboxylic acid containing a -Y carbon atom; - a copolymer {Z} selected from lactams and α,ω-aminocarboxylic acids containing Z carbon atoms, and an equimolar mixture of at least one diamine containing X1 carbon atoms and at least one dicarboxylic acid containing Y1 carbon atoms, (X1, Y1) being different from (X, Y), with said copolymer {Z}, which is incorporated in a weight proportion advantageously ranging up to 50%, preferably up to 20% and even more advantageously up to 10%, relative to the total amount of polyamide precursor monomers, -dicarboxylic acids.

[0068] Advantageously, a dicarboxylic acid containing Y carbon atoms is used as chain limiter, which is introduced in excess with respect to the stoichiometry of the diamine.

[0069] According to one variant of this third type, the polyamide blocks result from the condensation of at least two α,ω-aminocarboxylic acids, or at least two lactams containing from 6 to 12 carbon atoms, or one lactam and one aminocarboxylic acid not having the same number of carbon atoms, optionally in the presence of a chain limiter.

[0070] Examples of aliphatic α,ω-aminocarboxylic acids include aminocaproic acid, 7-aminoheptanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. Examples of lactams include caprolactam, enantholactam, lauryllactam, etc. Examples of aliphatic diamines include hexamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, etc.

[0071] Examples of cyclic aliphatic diacids include 1,4-cyclohexanedicarboxylic acid. Examples of aliphatic diacids include butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, dimerized fatty acids, etc. These dimerized fatty acids preferably have a dimer content of at least 98% and are preferably hydrogenated, such as the products sold under the brand name Pripol by Croda, the products sold under the brand name Empol by BASF, or the products sold under the brand name Radiacid by Oleon, and polyoxyalkylene α,ω-diacids. Examples of aromatic diacids include terephthalic acid (T) and isophthalic acid (I).

[0072] Examples of alicyclic diamines include bis(4-aminocyclohexyl)methane (BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM), 2,2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP), and isomers of paraaminodicyclohexylmethane (PACM). Other commonly used diamines can be isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN), piperazine.

[0073] Examples of polyamide blocks of the third type include: PA 6.6 / 6 (6.6 denotes a hexamethylenediamine unit condensed with adipic acid and 6 denotes a unit resulting from the condensation of caprolactam), -PA 6.6 / 6.10 / 11 / 12, (6.6 represents hexamethylenediamine condensed with adipic acid, 6.10 represents hexamethylenediamine condensed with sebacic acid, 11 represents units resulting from the condensation of aminoundecanoic acid, and 12 represents units resulting from the condensation of lauryllactam).

[0074] Designations such as PA X / Y, PA X / Y / Z relate to copolyamides where X, Y, Z etc. represent homopolyamide units as defined above.

[0075] Advantageously, the polyamide blocks of the copolymers used according to the invention are selected from the group consisting of the polyamides PA 6, PA 10, PA 11, PA 12, PA 5.4, PA 5.9, PA 5.10, PA 5.12, PA 5.13, PA 5.14, PA 5.16, PA 5.18, PA 5.36, PA 6.4, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 6.13, PA 6.14, PA 6.16, PA 6.18, PA 6.36, PA 10.4, PA 10.9, PA 10.10, PA 10.12, PA 10.13, PA 10.14, PA 10.16, PA 10.18, PA 10.36, PA 10.T, PA 12.4, PA 12.9, PA 12.10, PA 12.12, PA 12.13, PA 12.14, PA 12.16, PA 12.18, PA 12.36 or PA 12.T blocks, or mixtures or copolymers thereof, and preferably the polyamide PA 6, PA 10, PA 11, PA 12, PA 6.10, PA 6.12, PA 10.10 or PA 10.12 blocks, or mixtures or copolymers thereof, more preferably the polyamide PA 11, PA 12, PA 6 or PA 6.12 blocks, or mixtures or copolymers thereof.

[0076] The polyether blocks are formed from alkylene oxide units.

[0077] The polyether blocks may in particular be PEG (polyethylene glycol) blocks, i.e. blocks formed from ethylene oxide units, and / or PPG (propylene glycol) blocks, i.e. blocks formed from propylene oxide units, and / or PO3G (polytrimethylene glycol) blocks, i.e. blocks formed from polytrimethylene glycol ether units, and / or PTMG blocks, i.e. blocks formed from tetramethylene glycol units, also known as polytetrahydrofuran. PEBA copolymers contain several types of polyethers within their chains, the copolyethers possibly being in block or statistical form.

[0078] It is also possible to use blocks obtained by oxyethylation of bisphenols, for example bisphenol A. The latter products are described, inter alia, in EP 613 919.

[0079] The polyether blocks may also be composed of ethoxylated primary amines. Examples of ethoxylated primary amines include products of the formula: TIFF2025502728000001.tif42170, where m and n are integers between 1 and 20, and x is an integer between 8 and 18. These products are available on the market, for example, under the brand name Noramox® from the company CECA and under the brand name Genamin® from the company Clariant.

[0080] The polyether diol block is copolycondensed with the carboxy-terminated polyamide block. The general method for preparing PEBA copolymers containing ester bonds between the PA and PE blocks in two steps is known and described, for example, in FR 2846332. The general method for preparing PEBA copolymers with amide bonds between the PA and PE blocks is known and described, for example, in EP 1482011. The polyether block can also be mixed with a polyamide precursor and a chain-limited diacid to prepare a polymer containing polyamide blocks and polyether blocks with randomly distributed units (one-step process).

[0081] PEBAs can contain amine chain ends, provided that they also contain OH chain ends. PEBAs containing amine chain ends can result from the polycondensation of polyamide blocks having dicarboxyl chain ends and polyoxyalkylene blocks having diamine chain ends, for example, by cyanoethylation and hydrogenation of α,ω-dihydroxylated aliphatic polyoxyalkylene blocks, known as polyether diols.

[0082] It will be appreciated that the designation PEBA in this specification of the present invention relates not only to Pebax® products sold by Arkema, Vestamid® products sold by Evonik®, and Grilamid® products sold by EMS, but also to Pelestat® PEBA-type products sold by Sanyo, or other PEBAs from other suppliers.

[0083] Although the block copolymers mentioned above generally comprise at least one polyamide block and at least one polyether block, the present invention is also directed to copolymers comprising two, three, four (or more) different blocks selected from those described herein, provided that these blocks comprise at least a polyamide block and a polyether block.

[0084] For example, the copolymer according to the invention may be a segmented block copolymer comprising three different types of blocks (or a "triblock" copolymer), resulting from the condensation of several of the above blocks. The triblock may be, for example, a copolymer comprising a polyamide block, a polyester block and a polyether block, or a copolymer comprising a polyamide block and two different polyether blocks, such as a PEG block and a PTMG block. The triblock is preferably a copolyetheresteramide.

[0085] Particularly preferred PEBA copolymers according to the invention are copolymers comprising the following blocks: PA 10 and PEG; PA 10 and PTMG; PA 11 and PEG; PA 11 and PTMG; PA 12 and PEG; PA 12 and PTMG; PA 6.10 and PEG; PA 6.10 and PTMG; PA 6 and PEG; PA 6 and PTMG; PA 6.12 and PEG; PA 6.12 and PTMG.

[0086] The number average molar mass of the polyamide blocks in the PEBA copolymer is preferably 400 to 20,000 g / mol, more preferably 500 to 10,000 g / mol. In certain embodiments, the number average molar mass of the polyamide blocks in the PEBA copolymer is 400 to 500 g / mol, or 500 to 600 g / mol, or 600 to 1000 g / mol, or 1000 to 1500 g / mol, or 1500 to 2000 g / mol, or 2000 to 2500 g / mol, or 2500 to 3000 g / mol, or 3000 to 3500 g / mol, or 3500 to 4000 g / mol, or 4000 to 5000 g / mol, or 5000 to 6000 g / mol, or 6000 to 7000 g / mol, or 7000 to 8000 g / mol. 00-8000g / mol, or 8000-9000g / mol, or 9000-10000g / mol, or 10000-11000g / mol, or 11000-12000g / mol, or 12000-13000g / mol, or 13000-14000g / mol, or 14000-15000g / mol, or 15000-16000g / mol, or 16000-17000g / mol, or 17000-18000g / mol, or 18000-19000g / mol, or 19000-20000g / mol.

[0087] The number average molar mass of the polyether blocks is preferably 100-6000 g / mol, more preferably 200-3000 g / mol. In a particular embodiment, the number average molar mass of the polyether blocks is 100-200 g / mol, or 200-500 g / mol, or 500-800 g / mol, or 800-1000 g / mol, or 1000-1500 g / mol, or 1500-2000 g / mol, or 2000-2500 g / mol, or 2500-3000 g / mol, or 3000-3500 g / mol, or 3500-4000 g / mol, or 4000-4500 g / mol, or 4500-5000 g / mol, or 5000-5500 g / mol, or 5500-6000 g / mol.

[0088] The number average molar mass is determined by the content of the chain limiter and can be calculated according to the following formula: TIFF2025502728000002.tif10170

[0089] In this formula, n モノマー is the number of moles of monomer, n チェーンリミッター is the number of moles of excess diacid limiter, MW 繰り返し単位 is the molar mass of the repeating unit, MW チェーンリミッター represents the molar mass of the excess diacid.

[0090] The number-average molar masses of the polyamide blocks and of the polyether blocks can be determined by gel permeation chromatography (GPC) before the copolymerization of the blocks.

[0091] Advantageously, the weight ratio of the polyamide blocks to the polyether blocks of the copolymer is between 0.1 and 20, preferably between 0.5 and 18, and more preferentially between 0.6 and 15. This weight ratio can be calculated by dividing the number-average molar mass of the polyamide blocks by the number-average molar mass of the polyether blocks. In particular, the weight ratio of the polyamide blocks to the polyether blocks of the copolymer is between 0.1 and 0.2, or between 0.2 and 0.3, or between 0.3 and 0.4, or between 0.4 and 0.5, or between 0.5 and 0.6, or between 0.6 and 0.7, or between 0.7 and 0.8, or between 0.8 and 0.9, or between 0.9 and 1, or between 1 and 1.5, or between 1.5 and 2, or between 2 and 2.5, or between 2.5 and 3, or between 3 and 3.5, or between 3.5 and 4, or between 4 and 4. .5, or 4.5-5, or 5-5.5, or 5.5-6, or 6-6.5, or 6.5-7, or 7-7.5, or 7.5-8, or 8-8.5, or 8.5-9, or 9-9.5, or 9.5-10, or 10-11, or 11-12, or 12-13, or 13-14, or 14-15, or 15-16, or 16-17, or 17-18, or 18-19, or 19-20.

[0092] Advantageously, the polyamide block-polyether block copolymer has a Shore D hardness of at least 30. Preferably, at least one copolymer used according to the invention has an instantaneous Shore hardness of between 10D and 70D, preferably between 25D and 50D. The hardness measurement can be carried out in accordance with standard ISO 7619-1.

[0093] Advantageously, the PEBA of the present invention has an OH functional concentration of 0.002 meq / g to 0.2 meq / g, preferably 0.005 meq / g to 0.1 meq / g, more preferably 0.01 meq / g and 0.08 meq / g and / or a COOH functional concentration of 0.002 meq / g to 0.2 meq / g, preferably 0.005 meq / g to 0.1 meq / g, more preferably 0.01 meq / g to 0.08 meq / g. In particular, the PEBA of the present invention has an OH functional group concentration of 0.002 to 0.005 meq / g, or 0.005 to 0.01 meq / g, or 0.01 to 0.02 meq / g, or 0.02 to 0.03 meq / g, or 0.03 to 0.04 meq / g, or 0.04 to 0.05 meq / g, or 0.05 to 0.06 meq / g, or 0.06 to 0.07 meq / g, or 0.07 to 0.08 meq / g, or 0.08 to 0.09 meq / g, or 0.09 to 0.1 meq / g, or 0.1 to 0.15 meq / g, or 0.15 to 0.2 meq / g. and / or a COOH functional group concentration of 0.002-0.005 meq / g, or 0.005-0.01 meq / g, or 0.01-0.02 meq / g, or 0.02-0.03 meq / g, or 0.03-0.04 meq / g, or 0.04-0.05 meq / g, or 0.05-0.06 meq / g, or 0.06-0.07 meq / g, or 0.07-0.08 meq / g, or 0.08-0.09 meq / g, or 0.09-0.1 meq / g, or 0.1-0.15 meq / g, or 0.15-0.2 meq / g. The COOH functional group concentration can be determined by potentiometric analysis and the OH functional group concentration can be determined by proton NMR. For details of the measurement protocol, please refer to the paper "Synthesis and characterization of poly(copolyether-block-polyamides) - II. Characterization and properties of multiblock copolymers", Marechal et al., Polymer, Volume 41, 2000, 3561-3580.

[0094] Preferably, the polyamide blocks of the polyamide block-polyether block copolymers are polyamide 11, polyamide 12, polyamide 10, polyamide 6, polyamide 6.10, polyamide 6.12, polyamide 10.10 and / or polyamide 10.12, preferably polyamide 11, polyamide 12, polyamide 6 and / or polyamide 6.12 blocks; and / or the polyether blocks of the polyamide block-polyether block copolymers are polyethylene glycol and / or polytetrahydrofuran blocks.

[0095] [TPU] According to a variant, the rigid block is a polyamide comprising at least one Z or XY type unit, X is a polyisocyanate, ·Y is a chain extender.

[0096] The TPE copolymer is therefore in particular a thermoplastic polyurethane (TPU).

[0097] For purposes of this specification, a thermoplastic polyurethane is a copolymer comprising a rigid block and a flexible block, which is formed from the reaction of at least one polyisocyanate with at least one isocyanate-reactive compound, preferably comprising two isocyanate-reactive functional groups, more preferably a polyol, and optionally a chain extender, optionally in the presence of a catalyst.

[0098] The rigid TPU block is a block consisting of units derived from polyisocyanates and chain extenders, whereas the flexible block consists mainly of units derived from isocyanate-reactive compounds, preferably polyols, having a molar mass between 0.5 and 100 kg / mol.

[0099] The polyisocyanates may be aliphatic, cycloaliphatic, araliphatic and / or aromatic. Preferably, the polyisocyanates are diisocyanates.

[0100] Advantageously, the polyisocyanate is selected from the group consisting of tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 2-ethylbutylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-butylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 2,4-paraphenylene diisocyanate (PPDI), 2,4-tetramethylene xylene diisocyanate (TMXDI), 4,4'-, 2,4'- and / or 2,2'-dicyclohexylmethane diisocyanate (H12 The diisocyanate may be selected from the group consisting of 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or 1-methyl-2,6-cyclohexane diisocyanate, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate, phenylene diisocyanate, methylene bis(4-cyclohexyl isocyanate) (HMDI) and mixtures thereof.

[0101] More preferably, the polyisocyanate is selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), methylene bis(4-cyclohexylisocyanate) (HMDI), and mixtures thereof.

[0102] More preferably, the polyisocyanate is 4,4'-MDI (4,4'-diphenylmethane diisocyanate), 1,6-HDI (1,6-hexamethylene diisocyanate), or a mixture thereof.

[0103] The isocyanate-reactive compounds preferably have an average functionality between 1.8 and 3, more preferably between 1.8 and 2.6, and even more preferably between 1.8 and 2.2. The average functionality of the isocyanate-reactive compounds corresponds to the number of isocyanate-reactive functional groups of the molecules, theoretically calculated for one molecule from a certain amount of compound. Preferably, the isocyanate-reactive compounds have a Zerewitinoff active hydrogen number in the above range, according to a statistical average.

[0104] Preferably, the isocyanate-reactive compounds, preferably polyols, have a number-average molar mass of 500 to 100 000 g / mol. The isocyanate-reactive compounds may have a number-average molar mass in the range of 500 to 8 000 g / mol, preferably 700 to 6 000 g / mol and more particularly 800 to 4 000 g / mol.

[0105] In certain embodiments, the isocyanate-reactive compound has a molecular weight of 500-600 g / mol, or 600-700 g / mol, or 700-800 g / mol, or 800-1000 g / mol, or 1000-1500 g / mol, or 1500-2000 g / mol, or 2000-2500 g / mol, or 2500-3000 g / mol, or 3000-3500 g / mol, or 3500-4000 g / mol, or 4000-5000 g / mol, or 5000-6000 g / mol, or 6000-70 00g / mol, or 7000-8000g / mol, or 8000-10000g / mol, or 10000-15000g / mol, or 15000-20000g / mol, or 20000-30000g / mol, or 30000-40000g / mol, or 40000-50000g / mol, or 50000-60000g / mol, or 60000-70000g / mol, or 70000-80000g / mol, or 80000-100000g / mol. The number average molar mass can be measured by GPC, preferably according to standard ISO 16014-1:2012.

[0106] Advantageously, the isocyanate-reactive compound has at least one reactive group selected from hydroxyl, amine, thiol and carboxylic acid groups. Preferably, the isocyanate-reactive compound has at least one hydroxyl-reactive group, more preferably a plurality of hydroxyl groups. Thus, in a particularly advantageous manner, the isocyanate-reactive compound comprises or consists of a polyol.

[0107] Preferably, the polyol is selected from the group consisting of polyester polyols, polyether polyols, polycarbonate diols, polysiloxane diols, polyalkylene diols, and mixtures thereof. More preferably, the polyol is a polyether polyol, a polyester polyol, and / or a polycarbonate diol, so that the flexible blocks of the thermoplastic polyurethane are polyether blocks, polyester blocks, and / or polycarbonate blocks, respectively. Also preferably, the flexible blocks of the thermoplastic polyurethane are polyether blocks and / or polyester blocks (the polyol is a polyether polyol and / or a polyester polyol).

[0108] Polyester polyols include polycaprolactone polyols and / or copolyesters based on one or more carboxylic acids selected from adipic acid, succinic acid, pentanedioic acid and / or sebacic acid and one or more alcohols selected from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol and / or polytetrahydrofuran.

[0109] More specifically, the copolyesters may be based on adipic acid and a mixture of 1,2-ethanediol and 1,4-butanediol, or on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof, and polytetrahydrofuran (tetramethylene glycol), or mixtures of these copolyesters.

[0110] As the polyether polyol, a polyether diol (i.e., an aliphatic α,ω-dihydroxylated polyoxyalkylene block) is preferably used. Preferably, the polyether polyol is a polyether diol based on ethylene oxide, propylene oxide, and / or butylene oxide, a block copolymer based on ethylene oxide and propylene oxide, a polyethylene glycol, a polypropylene glycol, a polybutylene glycol, a polytetrahydrofuran, a polybutanediol, or a mixture thereof.

[0111] The polyether polyol is preferably polytetrahydrofuran (flexible block of thermoplastic polyurethane, hence polytetrahydrofuran block) and / or polypropylene glycol (flexible block of thermoplastic polyurethane, hence polypropylene glycol block) and / or polyethylene glycol (flexible block of thermoplastic polyurethane, hence polyethylene glycol block), preferably polytetrahydrofuran with a number average molar mass of 500 to 15000 g / mol, preferably 1000 to 3000 g / mol. The polyether polyol may be a polyether diol, which is a reaction product of ethylene oxide and propylene oxide, the molar ratio of ethylene oxide to propylene oxide being preferably 0.01 to 100, more preferably 0.1 to 9, more preferably 0.25 to 4, more preferably 0.4 to 2.5, more preferably 0.6 to 1.5, more preferably 1.

[0112] The polysiloxanediols that can be used in the present invention preferably have a number average molar mass of 500 to 15000 g / mol, preferably 1000 to 3000 g / mol. The number average molar mass can be determined by GPC, preferably according to standard ISO 16014-1:2012. Advantageously, the polysiloxanediol is a polysiloxane of formula (I): HO-[RO] n-R-Si(R')2-[O-Si(R')2] m -O-Si(R')2-R-[OR] p -OH (I) In the formula, R is preferably a C2-C4 alkylene, R' is preferably a C1-C4 alkyl, and n, m and p each independently preferably represent an integer between 0 and 50, with m more preferably in the range of 1 to 50, and even more preferably in the range of 2 to 50. Preferably, the polysiloxane has the following formula (II): TIFF2025502728000003.tif16170 [wherein Me is a methyl group] Or, the following formula (III): TIFF2025502728000004.tif17170

[0113] The polyalkylene diols that can be used in the present invention are preferably butadiene-based.

[0114] The polycarbonate diols that can be used in the present invention are preferably aliphatic polycarbonate diols. The polycarbonate diols are preferably based on alkanediols. They are preferably strictly difunctional. The preferred polycarbonate diols according to the present invention are based on butanediol, pentanediol and / or hexanediol, in particular 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane-(1,5)-diol, or mixtures thereof, more preferably based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or mixtures thereof. In particular, the polycarbonate diol may be a polycarbonate diol based on butanediol and hexanediol, a polycarbonate diol based on pentanediol and hexanediol, or a polycarbonate diol based on hexanediol, or a mixture of two or more of these polycarbonate diols. The polycarbonate diols advantageously have a number average molar mass ranging from 500 to 4000 g / mol, preferably from 650 to 3500 g / mol and even more preferably from 800 to 3000 g / mol. The number average molar mass can be determined by GPC, preferably according to standard ISO 16014-1:2012.

[0115] As isocyanate-reactive compounds, one or more polyols can be used.

[0116] In a particularly preferred manner, the flexible blocks of TPU are blocks of polytetrahydrofuran, polypropylene glycol, and / or polyethylene glycol.

[0117] Preferably, in addition to the isocyanate and the isocyanate-reactive compound, a chain extender (Y) is used in the preparation of the thermoplastic polyurethane.

[0118] The chain extenders may be aliphatic, araliphatic, aromatic and / or cycloaliphatic.

[0119] Advantageously, it has a number-average molar mass of 50 to 499 g / mol. The number-average molar mass can be measured by GPC, preferably according to standard ISO 16014-1:2012. The chain extender preferably has two isocyanate-reactive groups (also called "functional groups").

[0120] A single chain extender or a mixture of at least two chain extenders can be used.

[0121] The chain extender is preferably difunctional. Examples of chain extenders are diamines and alkanediols containing 2 to 10 carbon atoms. In particular, the chain extender may be selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, hydroquinone bis(beta-hydroxyethyl)ether (HQEE), di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or deca-alkylene glycols, their respective oligomers, polypropylene glycol, and mixtures thereof. More preferentially, the chain extender is selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and mixtures thereof, more preferably selected from 1,3-propanediol, 1,4-butanediol and / or 1,6-hexanediol.More preferably, the chain extender is a mixture of 1,4-butanediol and 1,6-hexanediol, more preferably in a molar ratio of 6:1 to 10:1.

[0122] Advantageously, the TPU is semi-crystalline. The melting point Tf is preferably between 100° C. and 230° C., more preferably between 120° C. and 160° C. The melting point can be measured according to standard ISO 11357-3, Plastics - Differential Scanning Calorimetry (DSC) Part 3.

[0123] Advantageously, the TPU may be a recycled TPU and / or a partially or fully bio-based TPU.

[0124] Preferably, the TPU has a Shore D hardness of less than or equal to 75, more preferably less than or equal to 65. In particular, the TPU used in the present invention may have a hardness of between 65 Shore A and 70 Shore D, preferably between 75 Shore A and 60 Shore D. The hardness measurement can be carried out in accordance with standard ISO 7619-1.

[0125] Advantageously, the TPU according to the invention has a concentration of OH functional groups between 0.002 meq / g and 0.6 meq / g, preferably between 0.01 meq / g and 0.4 meq / g and more preferably between 0.03 meq / g and 0.2 meq / g. In certain embodiments, the TPU according to the invention has an OH functional group concentration of 0.002-0.005 meq / g, or 0.005-0.01 meq / g, or 0.01-0.02 meq / g, or 0.02-0.04 meq / g, or 0.04-0.06 meq / g, or 0.06-0.08 meq / g, or 0.08-0.1 meq / g, or 0.1-0.2 meq / g, or 0.2-0.3 meq / g, or 0.3-0.4 meq / g, or 0.4-0.5 meq / g, or 0.5-0.6 meq / g. The OH functional group concentration can be measured by NMR under the conditions described in the following article: "Reactivity of isocyanates with urethanes:Conditions for allophanate formation",Lapprand et al.,Polymer Degradation and Stability,Volume 90,No.2,2005,363-373.

[0126] Advantageously, the rigid polyurethane block is composed of a diisocyanate chosen from 4,4'-MDI, HDI or PDI and / or a diol chosen from butanediol, propanediol, pentanediol and hexanediol.

[0127] [Thermoplastic polyester] Alternatively, the rigid block may be a polyester comprising at least one XY unit, X is a dicarboxylic acid, Y is a diol.

[0128] The thermoplastic copolyester elastomer comprises hard segments consisting of polyester repeat units derived from at least one aliphatic diol and at least one aromatic dicarboxylic acid or ester thereof, and soft segments selected from the group consisting of aliphatic polyethers, aliphatic polyesters, aliphatic polycarbonates, dimer fatty acids and dimer fatty diols, and combinations thereof.

[0129] The aliphatic diols generally contain 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms. These diols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butylene glycol, 1,2-hexanediol, 1,6-hexamethylenediol, 1,4-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and mixtures thereof. Preferably, 1,4-butanediol is used. Suitable aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, and mixtures thereof. Mixtures of 4,4'-diphenyldicarboxylic acid and 2,6-naphthalenedicarboxylic acid, or mixtures of 4,4'-diphenyldicarboxylic acid and terephthalic acid are also very suitable for use. The mixing ratio of 4,4'-diphenyldicarboxylic acid to 2,6-naphthalenedicarboxylic acid or 4,4'-diphenyldicarboxylic acid to terephthalic acid is preferably selected between 40:60 and 60:40 by weight to optimize the melting point of the thermoplastic copolyester.

[0130] The hard segments preferably have repeating units selected from the group consisting of ethylene terephthalate (PET), propylene terephthalate (PPT), butylene terephthalate (PBT), polyethylene bibenzoate, polyethylene naphthalate, polybutylene bibenzoate, polybutylene naphthalate, polypropylene bibenzoate, polypropylene naphthalate, and combinations thereof. Preferably, the hard segment is butylene terephthalate (PBT), because thermoplastic copolyester elastomers containing PBT hard segments have favorable crystallization behavior and high melting points, resulting in thermoplastic copolyester elastomers with good elastic properties and excellent heat and chemical resistance.

[0131] In one preferred embodiment, the composition comprises a thermoplastic copolyester elastomer having a rigid segment and a flexible segment, the rigid segment being selected from PBT or PET, preferably PBT, and the flexible segment being selected from the group consisting of polybutylene adipate (PBA), polyethylene oxide (PEG), polypropylene oxide (PPG), polytetramethylene oxide (PTMG), PEO-PPO-PEO, and combinations thereof, preferably PTMO, which results in a low density article. In another preferred embodiment, the composition comprises a copolyetherester thermoplastic elastomer consisting of PBT and PTMG.

[0132] Advantageously, the rigid polyester block is a polymer of terephthalic acid and butanediol.

[0133] Additives According to one embodiment, the composition also comprises from 0 to 5% by weight, preferably from 0.1% to 2% by weight, of additives relative to the total weight of the composition.

[0134] The additives may be selected from catalysts, antioxidants, heat stabilizers, UV stabilizers, light stabilizers, lubricants, flame retardants, nucleating agents, chain extenders, and dyes, among others.

[0135] Compatibilizer According to one embodiment, the composition comprises 0-5 wt%, 5-10 wt%, 10-15 wt%, 15-20 wt%, 20-25 wt%, 25-30 wt%, 30-35 wt%, or 25-40 wt% of a compatibilizer, based on the total weight of the composition.

[0136] Specifically, depending on the nature of the TPE and the rubber powder, the presence of a compatibilizer may be advantageous to obtain a good dispersion of the crosslinked rubber powder particles within the TPE matrix.

[0137] The term "compatibilizer" means an agent that promotes the compatibilization of the TPE matrix and the crosslinked rubber particles. It particularly refers to molecules, macromolecules, polymers or copolymers that have a good affinity with both the TPE matrix and the crosslinked rubber powder, which may promote physical cohesion between the various components of the composition or form chemical bonds with the matrix and / or the powder.

[0138] Physical cohesion may result, for example, from coatings of crosslinked rubber particles, entanglements of polymer and / or copolymer chains, and / or van der Waals or hydrogen bonding between all or some of the components of the composition.

[0139] In certain embodiments, at least a portion of the thermoplastic elastomer is covalently bonded to at least a portion of the compatibilizer via a urea, urethane, amide, ester, or alkoxysilane functional group. Preferably, an amount of the thermoplastic elastomer of 10% by weight or less, more preferably 5% by weight or less, is covalently bonded to at least a portion of the compatibilizer via a urea, urethane, amide, ester, or alkoxysilane functional group.

[0140] The compatibilizer preferably has reactive functional groups that can preferably react with alcohol, amine or carboxylic acid functional groups present in the thermoplastic elastomer.

[0141] The composition according to the invention may comprise one or more compatibilizers selected from copolyamides, impact modifiers, thermoplastic polyurethanes (TPUs), polymers containing silane groups, siloxanes, or mixtures thereof.

[0142] [Copolyamide] According to a particular embodiment, the compatibilizer may be selected from copolyamides, preferably comprising at least X / YZ or YZ / Y2Z2 units, X is an amino acid or lactam having between 6 and 18 carbon atoms, preferably between 6 and 12 carbon atoms; Y and Y2 are diamines having between 2 and 48 carbon atoms, preferably between 2 and 36 carbon atoms; Z and Z2 are dicarboxylic acids having between 6 and 48 carbon atoms, preferably between 6 and 36 carbon atoms.

[0143] In a particular embodiment, the copolyamide comprises fatty acid dimers having between 18 and 48 carbon atoms, preferably between 36 and 48 carbon atoms.

[0144] [Impact modifier] According to certain embodiments, the compatibilizer may be selected from compounds known as impact modifiers, which may be functionalized or non-functionalized.

[0145] The term "impact modifier" refers to a polymer that has a lower modulus than the resin, has good adhesion to the matrix, and dissipates cracking energy.

[0146] The impact modifier will advantageously be a polymer, in particular a polyolefin, with a flexural modulus of less than 100 MPa (measured according to standard ISO 178) and a Tg of less than 0° C. (measured at the inflection point of the DSC thermogram according to standard 11357-2).

[0147] The polyolefins of the impact modifier may be functionalized, unfunctionalized, or a mixture of at least one functionalized and at least one unfunctionalized. For simplicity, the polyolefins are designated (B) and functionalized polyolefins (B1) and unfunctionalized polyolefins (B2) are described below.

[0148] The non-functionalized polyolefins (B2) are generally homopolymers or copolymers of alpha-olefins or diolefins such as ethylene, propylene, 1-butene, 1-octene, butadiene, etc. Examples include: - Polyethylene homopolymers and copolymers, in particular LDPE, HDPE, LLDPE (Linear Low Density Polyethylene), VLDPE (Very Low Density Polyethylene) and metallocene polyethylene. - propylene homopolymer or copolymer. -Ethylene / alpha olefins such as ethylene / propylene, EPR (short for ethylene propylene rubber), and ethylene / propylene / diene (EPDM) copolymers. -Styrene / Ethylenebutene / Styrene (SEBS), Styrene / Butadiene / Styrene (SBS), Styrene / Isoprene / Styrene (SIS), Styrene / Ethylenepropylene / Styrene (SEPS) block copolymers. - copolymers of ethylene and at least one product chosen from salts or esters of unsaturated carboxylic acids, such as alkyl (meth)acrylates (for example methyl acrylate), or vinyl esters of saturated carboxylic acids, such as vinyl acetate (EVA), the proportion of comonomer being able to be up to 40% by weight;

[0149] The functionalized polyolefins (B1) may be polymers of α-olefins having reactive units (functional groups), such as acid, anhydride or epoxy functional groups. Examples include the aforementioned polyolefins (B2) grafted or copolymerized or terpolymerized with unsaturated epoxides, such as glycidyl (meth)acrylate, or with carboxylic acids or their salts or esters, such as (meth)acrylic acid, the latter of which may be fully or partially neutralized with metals, such as Zn, or with carboxylic anhydrides, such as maleic anhydride. The functionalized polyolefins are, for example, PE / EPR mixtures, the weight ratio of which may vary within a wide range, for example from 40 / 60 to 90 / 10, said mixtures being cografted with anhydrides, in particular maleic anhydride, the degree of grafting being, for example, from 0.01% to 5% by weight, advantageously from 2.8% to 5% by weight.

[0150] The functionalized polyolefin (B1) can be chosen from the following (co)polymers grafted with maleic anhydride or with glycidyl methacrylate, the degree of grafting being, for example, between 0.01% and 5% by weight: For example PE, PP, copolymers of ethylene with propylene, butene, hexene or octene, with an ethylene content of 35 to 80% by weight; -Ethylene / alpha olefins such as ethylene / propylene, EPR (short for ethylene propylene rubber), and ethylene / propylene / diene (EPDM) copolymers. -Styrene / Ethylenebutene / Styrene (SEBS), Styrene / Butadiene / Styrene (SBS), Styrene / Isoprene / Styrene (SIS), Styrene / Ethylenepropylene / Styrene (SEPS) block copolymers. - Ethylene and vinyl acetate copolymers (EVA) containing up to 40% by weight of vinyl acetate - Copolymers of ethylene and alkyl (meth)acrylates containing up to 40% by weight of alkyl (meth)acrylates, 15 -Copolymers of ethylene, vinyl acetate (EVA) and alkyl (meth)acrylates containing up to 40% by weight of comonomer.

[0151] The functionalized polyolefin (B1) can also be selected from ethylene / propylene copolymers based on propylene, grafted with maleic anhydride and then condensed with monoaminopolyamides (or polyamide oligomers) (products described in EP-A-20 0342066).

[0152] The functionalized polyolefin (B1) may be a copolymer or terpolymer of at least the following units: (1) ethylene, (2) an alkyl (meth)acrylate or a saturated carboxylic acid vinyl ester, and (3) an anhydride or anhydride such as maleic acid or (meth)acrylic acid, or an epoxy such as glycidyl (meth)acrylate.

[0153] Examples of the latter type of functionalized polyolefins include the following copolymers, in which ethylene preferably accounts for at least 60% by weight and the termonomer (functional group) accounts for, for example, 0.1% to 13% by weight of the copolymer: ethylene / alkyl(meth)acrylate / (meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymers, -ethylene / vinyl acetate / maleic anhydride or glycidyl methacrylate copolymers; - Copolymers of ethylene / vinyl acetate or alkyl (meth)acrylate / (meth)acrylic acid or maleic anhydride or glycidyl methacrylate.

[0154] In the aforementioned copolymers, the (meth)acrylic acid can be salified with Zn or Li.

[0155] The term "alkyl (meth)acrylate" in (B1) or (B2) means C1 to C8 alkyl methacrylates and acrylates, and may be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.

[0156] Furthermore, the above polyolefins (B1) may be crosslinked via any suitable process or agent (diepoxy, diacid, peroxide, etc.), and the term "functionalized polyolefin" also includes mixtures of the above polyolefins with difunctional agents such as diacids, dianhydrides, diepoxy, etc. that can react with these polyolefins, or mixtures of at least two functionalized polyolefins that can react together.

[0157] The above copolymers (B1) and (B2) can be copolymerized randomly or in a block form, and may have a linear or branched structure.

[0158] The molecular weight, MFI index and density of these polyolefins may also vary within wide limits that are recognizable to those skilled in the art. MFI is the abbreviation for Melt Flow Index. It is measured according to the standard ASTM 1238 or ISO 1133:2011.

[0159] The non-functionalized polyolefin (B2) is advantageously chosen from polypropylene homopolymers or copolymers and any ethylene homopolymer or copolymer of ethylene with a comonomer of higher alpha-olefin type such as butene, hexene, octene or 4-methyl-1-pentene. For example, PP, high density PE, medium density PE, linear low density PE, low density PE or very low density PE. These polyethylenes are known to those skilled in the art to be produced by "free radical" processes, by "Ziegler" type catalysis or, more recently, by "metallocene" catalysis.

[0160] The functionalized polyolefin (B1) is advantageously selected from any polymer containing α-olefin units and units with polar reactive functional groups, such as epoxy, carboxylic acid or carboxylic anhydride functional groups. Examples of polymers that may be mentioned include terpolymers of ethylene, alkyl acrylate, maleic anhydride or glycidyl methacrylate (such as the Lotader® products of SK Global Chemical), or polyolefins grafted with maleic anhydride (such as the Orevac® products of SK Global Chemical), and terpolymers of ethylene, alkyl acrylate and (meth)acrylic acid. Mention may also be made of polypropylene homopolymers or copolymers grafted with carboxylic anhydrides and then condensed with polyamides or monoamino oligomers of polyamides.

[0161] Advantageously, the impact modifier is a functionalized polyolefin (B1) having maleic anhydride or epoxide functional groups.

[0162] [TPU] According to a particular embodiment, the compatibilizer may be selected from thermoplastic polyurethanes. The TPUs useful as compatibilizers are as defined above for the TPE copolymers of the composition of the invention.

[0163] TPUs are commercially available, for example, from Covestro (Desmopan series) and BASF (Elastollan series).

[0164] [Silane] According to a particular embodiment, the compatibilizer may be selected from molecules or macromolecules containing silane or alkoxysilane groups. Advantageously, the molecules used contain one or more silane functional groups and functional groups selected from amine, hydroxyl, epoxide, carboxylic acid or maleic anhydride. For example, the following molecules can be used: (3-aminopropyl)triethoxysilane, triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane. Products of this type are sold by suppliers such as Gelest, Shin-Etsu, Dow Corning, Merck.

[0165] [Polysiloxane] According to a particular embodiment, the compatibilizer may be selected from polysiloxanes having the following structure: TIFF2025502728000005.tif37170

[0166] A may be selected from the group consisting of methyl, ethyl, propyl, isopropyl or pentyl, and preferably A is a methyl group.

[0167] Polysiloxanes are silicone oils of high molar mass (between 40 kg / mol and 40 kg / mol) and are commercially available in the form of masterbatches in various matrices.

[0168] An example of a commercially available polysiloxane is Dow Corning's MB 50 product.

[0169] The compatibilizer is very advantageously chosen from copolyamides, in particular those containing fatty acid dimers, impact modifiers, in particular functionalized maleic anhydrides or epoxides, TPUs, and mixtures thereof.

[0170] [Composition] According to a particular embodiment, when the composition comprises a PEBA copolymer and a TPU copolymer, the weight content of PEBA is greater than the weight content of TPU relative to the total weight of the composition.

[0171] Preferably, the compositions of the present invention do not contain any of the following: -crosslinked polyurethane (PU) particles, and / or thermoplastic SBS or SEBS, and / or -EPDM (Ethylene-Propylene-Diene Monomer) Terpolymer

[0172] The compositions according to the invention are thermoplastic, i.e. meltable.

[0173] The melting point of the composition is between 100 and 220°C, in particular between 120 and 190°C, preferably between 125 and 170°C.

[0174] Advantageously, the composition has a tan δ at 23 ° C. of less than or equal to 0.2, preferably less than or equal to 0.15, in particular less than 0.10. The tan δ (or loss factor) at 23 ° C. corresponds to the ratio of the loss modulus E ″ to the elastic modulus E ′ measured at a temperature of 23 ° C. by dynamic mechanical analysis (DMA). It can be measured according to the standard ISO 6721 of 2019, the measurement being carried out at a tensile strain of 0.1%, a frequency of 1 Hz and a heating rate of 2 ° C. / min. By tan δ, the elasticity of the composition can be characterized. The lower the tan δ, the greater the elastic recovery. The tan δ at 23 ° C. of the composition can be 0.05 to 0.06, or 0.06 to 0.07, or 0.07 to 0.08, or 0.08 to 0.09, or 0.09 to 0.10, or 0.10 to 0.11, or 0.10 to 0.15, or 0.15 to 0.2.

[0175] The coefficient of kinetic friction on a wet aluminum substrate, measured according to the procedure of SATRA TM 144:2011 at a speed of 50 mm / min up to an extension of 25 mm, is typically greater than 0.35, preferably greater than 0.45.

[0176] According to a second aspect, the invention relates to a method for preparing a composition as defined above, the process comprising the following steps: preferably in an extruder, advantageously in a co-kneader, o at least one TPE, preferably a copolymer, in the melt at 20% to 90% by weight, preferably 40% to 70% by weight, and o0.08m 2 / g and 100m 2 At least one crosslinked rubber powder having a specific surface area of ​​between 10% by weight and 80% by weight, preferably 30% by weight and 60% by weight, - 0 to 5%, preferably 0.1% to 4%, in particular 1% to 2% of additives; -0 to 40%, preferably 5 to 20%, in particular 10 to 15% and mixing the Optionally, forming the mixture into the form of granules, filaments or powder; and / or - Recovering the resulting composition. Includes.

[0177] The mixing step of the present method can be carried out by, inter alia, applying high shear, heat, or radiation to achieve good dispersion of the rubber powder particles within the thermoplastic elastomer matrix and produce a homogeneous mixture.

[0178] According to yet another aspect, the present invention relates to an article consisting of the aforementioned composition or consisting of at least one element comprising the aforementioned composition or comprising the aforementioned composition, said article being preferably a footwear component such as a shoe sole, which may be selected from footwear components which may preferably be dress shoes, indoor sports shoes (volleyball, badminton, etc.), outdoor sports shoes (trail running, hiking, football, skiing, etc.), water boots (surfing, kayaking, etc.), parts of ski poles, racket handles (tennis, badminton, etc.) and golf club handles, goalkeeper gloves (football, baseball, etc.), water equipment such as treadmills, diving boots, mask and snorkel parts, eyeglass frame parts (sleeves, temples, pads), ski mask frames, parts enabling vibration isolation of electronic devices and machines, external battery cases, automotive parts (seals, end caps), toys, watch bands, machine buttons (such as remote control buttons), seals, conveyor belt components.

[0179] Articles or elements made from the abovementioned compositions can in particular be produced by injection molding.

[0180] According to yet another aspect, the present invention relates to a method for recycling an article according to the invention, comprising the steps of: a) recovering, optionally after separation, at least a portion of said article made of a thermoplastic material comprising the composition of the present invention; b) grinding the thermoplastic material to obtain particles; c) melting the particles to obtain a molten mixture; d) optionally adding other ingredients to the molten mixture; e) optionally forming granules, filaments or powder from the molten mixture obtained at the end of step c) or step d); f) optionally forming the granules, filaments or powder; Includes.

[0181] Very advantageously, certain articles such as sports shoes comprising a sole made of a composition according to the invention do not require a step of separating the various components in step a) and they can be directly ground and melted to form new articles made of recycled thermoplastic material, for example new soles for sports shoes, which represents a major economic and environmental advantage over the composite materials currently used for sports shoes etc., which are difficult to recycle.

[0182] According to yet another aspect, the invention relates to granules, filaments or powder obtainable by the recycling method according to the claims.

[0183] According to yet another aspect, the invention relates to an article consisting of or comprising at least one element prepared from granules, filaments or powder obtained by the recycling method according to the claims.

[0184] The article is, for example, the sole of a shoe, in particular a sports shoe.

[0185] definition Throughout the description, the terms listed below have the following meanings:

[0186] Throughout the description, the term "polyamide" (PA) refers to homopolyamides or copolyamides, i.e. condensation products of polyamide monomers, in particular lactams, α,ω-aminocarboxylic acids and / or dicarboxylic acids with diamines.

[0187] In this description of polyamides, the term "monomer" should be taken to mean "repeating unit". It is particularly preferred when the repeating units of the polyamide consist of a combination of dicarboxylic acid and diamine. The equivalent of a monomer is considered to be a combination of diamine and dicarboxylic acid, i.e. a diamine-diacid pair (in equimolar amounts). This is explained by the fact that dicarboxylic acid or diamine individually are merely structural units and are insufficient by themselves to polymerize. When the polyamides according to the invention comprise at least two different monomers, known as "comonomers", i.e. at least one monomer and at least one comonomer (a monomer different from the first monomer), they comprise copolymers, such as copolyamides (abbreviated COPA). Copolyamides thus result from the polycondensation of several monomers forming polyamide units.

[0188] The nomenclature used to define polyamides is described in the standard ISO 1874-1:1992 "Plastics-Polyamide (PA) molding and extrusion materials - Part 1: Designation", in particular on page 3 (tables 1 and 2) and is well known to the skilled person. In the PAL notation, PA stands for polyamide and L stands for the number of carbon atoms of the α,ω-amino carboxylic acid or lactam. Thus, polyamides are obtained by polycondensation of α,ω-amino carboxylic acids or lactams containing L carbon atoms. In the PAMN notation, M stands for the number of carbon atoms of the diamine and N for the number of carbon atoms of the dicarboxylic acid.

[0189] The α,ω-aminocarboxylic acids include C6 to C18 α,ω-aminocarboxylic acids, in particular aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

[0190] Examples of lactams include C6 to C18 lactams, particularly caprolactam, enantholactam, and lauryllactam.

[0191] Examples of dicarboxylic acids include linear or branched aliphatic, alicyclic or aromatic C6 to C18 dicarboxylic acids, in particular 1,4-cyclohexanedicarboxylic acid, butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, terephthalic acid and isophthalic acid, but also dimerized fatty acids.

[0192] Examples of diamines include linear or branched aliphatic, cyclic, saturated or unsaturated C2-C18 diamines, in particular tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, bis(4-aminocyclohexyl)methane (BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM) and the isomers of 2,2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP), and paraaminodicyclohexylmethane (PACM), and isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN) and piperazine (Pip).

[0193] The term "copolymer" refers to a polymer resulting from the copolymerization of at least two chemically different monomers, called comonomers. A copolymer is thus formed from at least two different repeat units. It may also be formed from three or more repeat units. More specifically, the term "block copolymer" refers to a copolymer in the above sense, in which at least two different monomer blocks are covalently linked. The length of the block is variable. Preferably, a block is composed of 1 to 1000, preferably 1 to 100, in particular 1 to 50 repeat units. The link between the two monomer blocks may require an intermediate non-repeating unit, called a junction block.

[0194] The term "melting point" means the temperature at which a partially crystalline polymer transitions into a viscous liquid state, measured on the first heating (Tf1) by differential scanning calorimetry (DSC) at a heating rate of 20° C. / min in accordance with standard NF EN ISO 11 357-3.

[0195] It is further pointed out that, unless otherwise specified, physical quantities are measured under standard temperature and pressure conditions, specifically 23° C. and atmospheric pressure.

[0196] The term "thermoplastic polymer" refers to a polymer that has the property of softening when heated sufficiently and hardening again when cooled.

[0197] The physical quantities which are particularly useful for characterizing the mechanical properties of the compositions according to the invention are defined as follows: - The tensile modulus is measured according to standard ISO 527-1A, The stress at -50% strain is measured according to standard ISO 527-1A, - The elongation at break is measured according to standard ISO 527-1A, - The breaking stress is measured according to standard ISO 527-1A, - Abrasion resistance is measured according to DIN 53516 - The coefficient of kinetic friction on the substrate is measured according to procedure SATRA TM 144:2011 at a speed of 50 mm / min up to an elongation of 25 mm, - Shore A or D hardness is measured after 3 seconds according to standard ISO 7619-1, -Recyclability is evaluated according to the melting or non-melting properties of the composition.

[0198] It is further specified that the expressions "between... and..." and "from... to..." as used in this specification are to be understood as including each referenced limitation.

[0199] Unless otherwise stated, percentages are expressed on a weight basis relative to the total weight of the composition. EXAMPLES

[0200] Working Example The following examples illustrate the invention without limiting it.

[0201] The following polymers were used: PEBA No. 1: PEBA copolymer comprising a PA 11 block with a number average molar mass of 600 g / mol and a flexible PTMG block with a number average molar mass of 1000 g / mol and a Shore D hardness of 25. PEBA No. 2: PEBA copolymer comprising a rigid PA 12 block with a number average molar mass of 600 g / mol and a PTMG block with a number average molar mass of 2000 g / mol and a Shore D hardness of 33. - Elastollan® 1185A: A thermoplastic polyurethane commercially available from BASF. - Kraton® FG1901: A triblock copolymer of styrene and ethylene / butylene with a polystyrene content of 30% and a branched maleic anhydride content between 1.4% and 2%, commercially available from Kraton. - Lotader® AX8900 is a random copolymer of ethylene, acrylic esters and glycidyl methacrylate, sold by SK Chemicals. - TyreXol® CW50 is commercially available from TRS, 0.12 m 2 The rubber powder is derived from used tires and has a specific surface area of ​​1.0 μm / g. The D50 diameter of this powder is 130 μm and the D90 is 270 μm.

[0202] Various compositions were prepared, the contents of whose components in percentage by weight are shown in Table 1 below. TIFF2025502728000006.tif59170

[0203] The compositions EC2 to EI4 were produced using a ZSK 18 mm twin screw extruder (manufactured by Coperion). The barrel temperature was set at 180° C., the screw speed was 280 rpm, and the flow rate was 8 kg / h.

[0204] Compositions EI5 to EI8 were produced using a PR46 co-kneader (Buss). The barrel and intake screw temperatures were set at 175° C. The co-kneader speed was set at 250 rpm, the intake screw at 20 rpm and the flow rate was 15 kg / h.

[0205] Composition EC1 is a crosslinked synthetic rubber sheet.

[0206] The composition was then dried under reduced pressure at 80° C. so that the moisture content was less than 0.04%.

[0207] The 1A test specimens (according to standard ISO 527), 6 mm sheets, and 2 mm sheets were produced by injection molding using a Battenfeld BA800 CDC press and an unpolished mold. The following parameters were applied during injection: -Barrel temperature: 150℃ -Nozzle temperature: 170℃ -Mold temperature: 20℃ -Cycle time: 60 seconds

[0208] Various properties of these compositions were evaluated. - the coefficient of kinetic friction on a wet aluminium plate measured according to procedure SATRA TM 144:2011 at a speed of 50 mm / min up to an elongation of 25 mm, -Recyclability is evaluated according to the meltability or non-meltability of the composition: if the composition is meltable, i.e. it turns into a molten fluid under the influence of heat, it is classified as (+), if the composition is not meltable it is classified as (-).

[0209] All of these evaluations were performed on dry (unconditioned) specimens.

[0210] The results are shown in Table 2 below. TIFF2025502728000007.tif29170

[0211] Compositions according to the invention are recyclable (meltable) and have been found to have a high dynamic coefficient of friction on wet aluminum substrates, providing excellent anti-slip properties.

Claims

1. based on the total weight of the composition, - 20% to 90% by weight, preferably 40% to 70% by weight, of at least one thermoplastic elastomer (TPE), preferably an elastomeric thermoplastic copolymer; ・0.08m ２ / g and 100m ２ / g, preferably between 0.1 and 80 m ２ / g, more preferably between 0.1 and 50 m ２ 10% by weight to 80% by weight, preferably 30% by weight to 60% by weight, of at least one crosslinked rubber powder having a specific surface area of ​​between 10% by weight and 80% by weight, and 10% by weight to 80% by weight, preferably 30% by weight to 60% by weight, Additives in an amount of 0 to 5%, preferably 0.1% to 4%, in particular 1% to 2%, Compatibilizer: 0 to 40%, preferably 5 to 20%, especially 10 to 15% A composition comprising:

2. The crosslinked rubber powder is 0.08 m ２ / g and 0.5m ２ / g, preferably between 0.1 and 0.3 m ２ / g, more preferentially between 0.1 and 0.2 m ２ 10. The composition of claim 1, having a specific surface area of ​​between 1000 and 10000 kJ / g.

3. 2. The composition according to claim 1, wherein the crosslinked rubber powder has a median diameter D50 between 2 μm and 500 μm, preferably between 50 μm and 300 μm, and more preferentially between 60 μm and 200 μm.

4. 2. The composition according to claim 1, having a D90 diameter between 10 and 800 μm, preferably between 80 and 500 μm, and more preferentially between 100 and 300 μm.

5. 2. The composition of claim 1, wherein the rubber of the crosslinked rubber crumb is a natural or synthetic rubber or a mixture thereof.

6. 2. The composition according to claim 1, wherein the rubber of the crosslinked rubber powder comprises 10% to 80% by weight, preferably 15% to 70% by weight, of natural rubber.

7. The composition of claim 4, wherein the natural rubber is cis-1,4-polyisoprene or trans-1,4-polyisoprene.

8. 2. Composition according to claim 1, wherein the crosslinked rubber powder comprises styrene butadiene rubber in a content preferably greater than 5% by weight, and more preferentially greater than 10% by weight.

9. 10. The composition of claim 1, wherein the crosslinked rubber crumb is derived from used tires.

10. 10. The composition of claim 1, wherein the crosslinked rubber crumb is obtained by water jet cutting of tires.

11. 2. Composition according to claim 1, wherein the crosslinked rubber powder comprises from 1% to 70%, preferably from 5% to 50%, and more preferentially from 10% to 40%, of carbon black and / or silica.

12. 2. The composition of claim 1, wherein the at least one TPE is selected from polyamide elastomers, thermoplastic polyurethanes, polyester elastomers, styrene-butadiene block copolymers, and styrene-ethylene-butadiene block copolymers, and mixtures thereof, preferably selected from polyamide elastomers, thermoplastic polyurethanes, and polyester elastomers, and mixtures thereof.

13. 2. The composition according to claim 1, wherein the TPE comprises flexible polyether and / or polyester blocks, preferably polyether, and more preferentially PTMG, and / or rigid blocks chosen from polyamide, polyurethane and polyester.

14. A polyamide wherein the rigid block comprises at least one Z-type unit or XY-type unit, Z is a lactam or amino acid containing 6 to 18 carbon atoms; X is a diamine containing 4 to 48 carbon atoms; Y is a diacid containing 6 to 48 carbon atoms; The composition of claim 12.

15. a polyurethane in which the rigid block comprises at least one XY unit; X is a diisocyanate, Y is a diol, The composition of claim 12.

16. a polyester in which the rigid block comprises at least one XY unit; X is a dicarboxylic acid, - Y is a diol The composition of claim 12.

17. 13. The composition according to claim 12, wherein the ratio of flexible blocks to rigid blocks is selected so that the tensile modulus according to ISO 527 is between 5 MPa and 800 MPa, preferably between 10 MPa and 300 MPa, and more preferentially between 20 MPa and 150 MPa.

18. 2. The composition according to claim 1, wherein the TPE has a Shore hardness between 10D and 70D, preferably between 25D and 50D.

19. 18. A method for preparing a composition according to any one of claims 1 to 17, comprising: Preferably in an extruder, 20% to 90% by weight, preferably 40% to 70% by weight, of at least one thermoplastic elastomer TPE, preferably a copolymer, in the molten state, 0.08m ２ / g and 100m ２ / g, preferably between 0.1 and 80 m ２ / g, more preferentially between 0.1 and 50 m ２ 10% by weight to 80% by weight, preferably 30% by weight to 60% by weight, of at least one crosslinked rubber powder having a specific surface area of ​​between 10% by weight and 80% by weight, and 10% by weight to 80% by weight, preferably 30% by weight to 60% by weight, o additives in an amount of 0 to 5%, preferably 0.1% to 4%, in particular 1% to 2%; The compatibilizer is 0 to 40%, preferably 5 to 20%, particularly 10 to 15%. mixing the Optionally, forming the mixture into the form of granules, filaments or powder; and / or - Recovering the resulting composition A method comprising:

20. 18. An article comprising at least one element comprising the composition of any one of claims 1 to 17, said article preferably being selected from footwear components such as shoe soles, ski pole parts, racket and golf club handles, goalkeeper gloves, sporting goods parts such as treadmills, underwater equipment such as diving boots, masks and snorkel parts, eyeglass frame parts (sleeves, temples, nose pads), ski mask frames, vibration isolation parts for electronic devices and machines, external battery shells, automotive parts (seals, end caps), toys, watch bands, machine buttons, seals or conveyor belt components.

21. 21. A method of manufacturing the article of claim 20, comprising: - a process for the composition according to any one of claims 1 to 17, - injection molding said composition; A method comprising:

22. 21. A method for recycling an article according to claim 20, comprising: a) recovering, optionally after separation, at least a portion of the article made of a thermoplastic material comprising the composition according to any one of claims 1 to 17; b) grinding the thermoplastic material to obtain particles; c) melting the particles to obtain a molten mixture; d) optionally adding other ingredients to the molten mixture; e) optionally forming granules, filaments or powder from the molten mixture obtained at the end of step c) or step d); f) optionally shaping the granules, filaments or powder; A method comprising:

23. Granules, filaments or powder obtainable according to the method for recycling according to claim 22.

24. 24. An article comprising at least one element prepared from the granules, filaments or powder of claim 23.