Composition containing a copolymer of polyamide blocks and polyether blocks 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 polyamide block-polyether block copolymer in an amount of 20% to 90% by weight, preferably 40% to 70% by weight, at least one crosslinked rubber powder, in particular from used tires, in an amount of 10% to 80% by weight, preferably 30% to 60% by weight, Additives: 0-5%, preferably 0.1%-4%, in particular 1%-2%; Compatibilizer: 0-40%, preferably 5-20%, in particular 10-15%.

Description

[Technical field]

[0001] The present invention relates to a composition based on polyamide block-polyether block copolymers and crosslinked rubber powder, in particular obtained by grinding used tires, and to a process for its manufacture.The invention also relates to articles, such as shoe soles, which consist of or contain elements made of such compositions or which contain such compositions, to a process for their manufacture and to a process for recycling them.The invention also relates to the granules, filaments or powder obtained by this recycling process, and to the articles prepared therefrom. [Background technology]

[0002] Polymer compositions used in the field of sports equipment, such as shoe soles or sole parts, gloves, rackets or golf balls, or in particular personal protective equipment for sports (vests, inner parts of helmets, shells, etc.), must satisfy a number of requirements, in particular with regard to rebound strength, low residual tensile strain and the ability to withstand repeated impacts and return to their original shape.

[0003] WO 17 / 021164 A describes a composition comprising a rubber powder, a thermoplastic polyurethane obtained from a polyisocyanate and a polyol, and a polysiloxane. This composition can be used, in particular, for shock absorption in shoe soles.

[0004] 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 properties. Summary of the Invention

[0005] The present invention relates first to a composition comprising the following components based on the total weight of the composition: - at least one polyamide block polyether block copolymer in an amount of 20% to 90% by weight, preferably 40% to 70% by weight, - 10% to 80% by weight, preferably 30% to 60% by weight, of at least one crosslinked rubber powder, in particular recycled from used tires, - 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.

[0006] In certain embodiments of the composition, - Crosslinked rubber powder is 0.01m 2 / g and 100m 2 / g, the crosslinked rubber powder has an average particle size D50 between 2 μm and 500 μm, preferably between 50 μm and 300 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 comprises 0 to 50% by weight, preferably 5% to 40% by weight, of a synthetic rubber or a mixture of synthetic rubbers, 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 by cutting tires with a water jet, 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 crosslinked rubber powder comprises less than 10%, advantageously less than 5% and very advantageously less than 1% of fibrous material, the crosslinked rubber powder advantageously contains between 0.05% and 5% by weight, preferably between 0.1% and 2.5% by weight, of zinc oxide, the additives are selected from catalysts, antioxidants, heat stabilizers, UV stabilizers, light stabilizers, lubricants, flame retardants, nucleating agents, chain extenders and dyes; at least one polyamide block-polyether block copolymer has a Shore hardness between 10D and 70D, preferably between 25D and 50D, 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.

[0007] 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 polyamide block polyether block copolymer in the melt at 20% to 90% by weight, preferably 40% to 70% by weight, o at least one crosslinked rubber powder, in particular from used tires, from 10% to 80% by weight, preferably from 30% to 60% by weight, o 0 to 5% of additives, preferably 0.1% to 4%, particularly 1% to 2%, 0 to 40%, preferably 5 to 20%, particularly 10 to 15% of a compatibilizer; mixing the Optionally, forming the mixture into the form of granules, filaments or powder, and / or - Recovering the resulting composition. Includes.

[0008] The present invention also relates to an article consisting of or comprising at least one element consisting of the composition according to the invention or comprising the composition according to the invention, said article being preferably selected from footwear components such as shoe soles, ski pole parts, racket and golf club handles, goalkeeper gloves, treadmills, diving boots, underwater equipment such as 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.

[0009] The present invention also relates to a method for producing an article according to claim 18, 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:

[0010] The present invention also relates to a method for recycling an article according to the invention, comprising the following successive steps: a) recovering at least a portion of said article made of a thermoplastic material comprising the composition of the present invention, optionally after separation; 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; The present invention relates to a method comprising the steps of:

[0011] The present invention also relates to the granules, filaments or powder obtained according to the recycling method according to the invention.

[0012] The invention also relates to an article consisting of or comprising at least one element prepared from the granules, filaments or powder according to the invention.

[0013] 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 (measured by the coefficient of friction) and good tensile properties. The composition has good elastic recovery, low density, high elongation at break, good adhesion to wet surfaces and, due to its meltability, can be recycled into other materials.

[0014] In particular, the inventors have been able to observe that these compositions have a lower tangent delta than prior art compositions, a feature that is particularly advantageous when used in the soles of sports shoes, since the composition consumes less energy, allowing the runner to run faster.

[0015] This is achieved by using specific amounts of at least one polyamide block polyether block copolymer (PEBA) and at least one crosslinked rubber powder, in particular from used tires. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The invention is explained in more detail and in a non-limiting manner in the following description.

[0017] Thus, according to a first aspect, the invention relates to a composition comprising, relative to the total weight of the composition: at least one polyamide block-polyether block copolymer in an amount of 20% to 90% by weight, preferably 40% to 70% by weight, at least one crosslinked rubber powder, in particular from used tires, in an amount of 10% to 80% by weight, preferably 30% to 60% by weight, Additives: 0-5%, preferably 0.1%-4%, in particular 1%-2%; Compatibilizer: 0-40%, preferably 5-20%, particularly 10-15% The present invention relates to a composition comprising:

[0018] Crosslinked rubber powder The crosslinked rubber powder used in the composition of the present invention can be characterized by a particular specific surface area.

[0019] According to a preferred embodiment, the specific surface area of ​​the crosslinked rubber powder is 0.01 m 2 / g and 100m 2 / g, especially 0.01m 2 / g and 80m 2 / g, especially 0.01m 2 / g and 50m 2 / g, most especially between 0.01 and 10m 2 / g, advantageously 0.03m 2 / g and 0.50m 2 According to another embodiment, the specific surface area is between 0.01 and 0.50 m 2 / g, especially 0.05m 2 / g and 0.30m 2 / g, preferably 0.08m 2 / g and 0.20m 2 / g, more preferably between 0.1 and 0.2 m 2 / g.

[0020] The specific surface area is measured by the BET method described in Shen et al., Constr. Build. Mater. 2009, 23(1), 304-310.

[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 machines such as the RX-94Duo 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] In this specification, the term "crosslinked rubber" means crosslinked natural rubber and / or crosslinked synthetic rubber (elastomer).

[0028] The rubbers used in the manufacture of crosslinked rubber powders 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.

[0029] 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.

[0030] The rubber of the crosslinked rubber powder may contain 10% to 80% by weight, and preferably 15% to 70% by weight, of natural rubber.

[0031] The natural rubber may in particular be chosen from cis-1,4-polyisoprene or trans-1,4-polyisoprene.

[0032] The rubber of the crosslinked 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.

[0033] Crosslinked rubber powder can be obtained from various sources, especially from the recycling of industrial waste and finished products after use. Such objects can come from many sectors: clothing, especially shoe outsoles and boots, automotive, sealing parts such as gaskets, airbags, floor mats, anti-vibration supports and fittings, industrial, conveyor belts, belts, drinking water seals, O-rings, cables, pipes, etc.; for the general public: window seals, mattress foams, golf balls, tennis balls, windsurfing suits, masks, fins; for construction: earthquake-resistant bridges and pads, flexible tanks and profiles; for hygiene and medical: gloves and baby bottle nipples.

[0034] The crosslinked rubber powder is characterized in that it is obtained from the recycling of used products. This may in particular include used tires, tires at the end of their life and / or tires that have traveled at least 20 km. Recycled crosslinked rubber, in particular 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.

[0035] Without being bound to a particular theory, these polar functionalities may improve the interaction between the thermoplastic PEBA-based matrix and the crosslinked rubber powder particles, enhancing the physical properties of the composite.

[0036] One example of a source of crosslinked rubber crumb obtained from used tires is the rubber compounds recovered during grinding of vehicle tire treads during regrooving procedures, however, as noted above, rubber may be obtained from a variety of sources, including whole tires, tire sidewalls, tire innerliners, tire carcasses, power transmission belts, conveyor belts, pipes, and various other rubber products.

[0037] 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.

[0038] 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, powder pulverization, etc. Water jet grinding (also called waterjet chopping) is particularly suitable for used tires.

[0039] 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.

[0040] In one embodiment, the crosslinked rubber powder comprises carbon black and silica, the silica content being advantageously twice, and very advantageously five times, the carbon black content, expressed as a weight content relative to the total weight of the composition.

[0041] Furthermore, the crosslinked rubber powder may contain less than 10%, advantageously less than 5%, and very advantageously less than 1% of fibrous material.

[0042] Preferably, the composition is free of glass fibers.

[0043] Furthermore, the crosslinked rubber powder may contain 0.05% to 5% by weight, preferably 0.1% to 2.5% by weight, of zinc oxide.

[0044] Polyamide block-polyether block copolymer (PEBA) 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.

[0045] 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.

[0046] Three types of polyamide blocks can be advantageously used.

[0047] 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.

[0048] 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.

[0049] Examples of diamines include tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, bis(4-aminocyclohexyl)methane (BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM) and isomers of 2,2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP), paraaminodicyclohexylmethane (PACM), isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN) and piperazine (Pip).

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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).

[0059] 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.

[0060] 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).

[0061] Designations such as PA X / Y, PA X / Y / Z relate to copolyamides where X, Y, Z etc. represent homopolyamide units as defined above.

[0062] 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.

[0063] The polyether blocks are formed from alkylene oxide units.

[0064] 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.

[0065] 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.

[0066] The polyether blocks may also be composed of ethoxylated primary amines. Examples of ethoxylated primary amines include products of the formula: TIFF2025501595000001.tif40170, 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.

[0067] 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).

[0068] 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.

[0069] It goes without saying 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® type PEBA products sold by Sanyo, or other PEBAs from other suppliers.

[0070] 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.

[0071] For example, the copolymer 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] The number average molar mass is determined by the content of the chain limiter and can be calculated according to the following formula: TIFF2025501595000002.tif7170

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] Specifically, depending on the nature of the PEBA 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 PEBA copolymer matrix.

[0086] The term "compatibilizer" refers to an agent that allows the compatibilization of the PEBA copolymer matrix and the crosslinked rubber particles. It specifically refers to molecules, macromolecules, polymers, or copolymers that have a good affinity with both the PEBA copolymer-matrix and the crosslinked rubber powder, which may promote physical cohesion between the various components of the composition and / or form chemical bonds with the matrix and / or the powder.

[0087] 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.

[0088] In one embodiment, the compatibilizer is at least partially covalently bonded to the matrix and / or to the rubber powder. The groups that bond the compatibilizer to the matrix and / or to the powder may be urea groups, urethane groups, amide groups, ester groups or alkoxysilane groups.

[0089] 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.

[0090] The compatibilizer preferably has reactive functional groups that can preferably react with alcohol, amine or carboxylic acid functional groups present in the thermoplastic elastomer.

[0091] The composition according to the invention may comprise one or more compatibilizers selected from copolyamides, compounds known as impact modifiers, thermoplastic polyurethanes (TPUs), polymers containing silane groups, siloxanes, or mixtures thereof.

[0092] [Copolyamide] According to a particular embodiment, the compatibilizer may be chosen from copolyamides, in particular those of formula X / YZ or of units YZ / Y 2 Z 2 [In the formula, X is an aliphatic α,ω-aminocarboxylic acid or lactam having 6 to 18, preferably 6 to 12, carbon atoms; Y and Y 2is a diamine having 2 to 48 carbon atoms, preferably 2 to 36 carbon atoms, Z and Z 2 is a dicarboxylic acid having 6 to 48 carbon atoms, preferably 6 to 36 carbon atoms.

[0093] In a particular embodiment, the copolyamide comprises fatty acid dimers having from 18 to 48 carbon atoms, preferably from 36 to 48 carbon atoms.

[0094] [Impact modifier] According to certain embodiments, the compatibilizer may be selected from functionalized or non-functionalized impact modifiers.

[0095] 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.

[0096] Advantageously, the impact modifier is a polymer, in particular a polyolefin, having 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).

[0097] 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.

[0098] 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;

[0099] The functionalized polyolefins (B1) may be polymers of α-olefins having reactive units (functional groups), which may in particular be 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 an anhydride, in particular maleic anhydride, the degree of grafting being, for example, from 0.01% to 5.8% by weight, advantageously from 2.8% to 5% by weight.

[0100] 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.

[0101] - 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; -Copolymers of ethylene, vinyl acetate (EVA) and alkyl (meth)acrylates containing up to 40% by weight of comonomer.

[0102] 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).

[0103] 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 such as maleic or (meth)acrylic anhydride, or an epoxy such as glycidyl (meth)acrylate.

[0104] 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.

[0105] In the aforementioned copolymers, the (meth)acrylic acid can be salified with Zn or Li.

[0106] 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.

[0107] 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.

[0108] The above copolymers (B1) and (B2) can be copolymerized randomly or in a block form, and may have a linear or branched structure.

[0109] 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.

[0110] 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 catalysts or, more recently, by "metallocene" catalysts.

[0111] 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.

[0112] Advantageously, the impact modifier is a functionalized polyolefin (B1) having maleic anhydride or epoxide functional groups.

[0113] [TPU] According to a particular embodiment, the compatibilizer may be selected from thermoplastic polyurethanes (TPUs).

[0114] Thermoplastic polyurethanes are copolymers containing rigid and flexible blocks, which are formed from the reaction of at least one polyisocyanate with at least one isocyanate-reactive compound, preferably containing two isocyanate-reactive functional groups, more preferably a polyol, and optionally a chain extender, optionally in the presence of a catalyst.

[0115] 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.

[0116] The polyisocyanates may be aliphatic, cycloaliphatic, araliphatic and / or aromatic. Preferably, the polyisocyanates are diisocyanates.

[0117] 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.

[0118] 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.

[0119] More preferably, the polyisocyanate is 4,4'-MDI (4,4'-diphenylmethane diisocyanate), 1,6-HDI (1,6-hexamethylene diisocyanate), or a mixture thereof.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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).

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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 C 2 ~C 4 alkylene, R' is preferably C 1 ~C 4 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): TIFF2025501595000003.tif16170 [wherein Me is a methyl group] Or, the following formula (III): TIFF2025501595000004.tif14170

[0130] The polyalkylene diols that can be used in the present invention are preferably butadiene-based.

[0131] 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.

[0132] As isocyanate-reactive compounds, one or more polyols can be used.

[0133] In a particularly preferred manner, the flexible blocks of TPU are blocks of polytetrahydrofuran, polypropylene glycol, and / or polyethylene glycol.

[0134] Preferably, a chain extender is used in addition to the isocyanate and the isocyanate-reactive compound in the production of the thermoplastic polyurethane.

[0135] The chain extenders may be aliphatic, araliphatic, aromatic and / or cycloaliphatic.

[0136] 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").

[0137] A single chain extender or a mixture of at least two chain extenders can be used.

[0138] 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.

[0139] Advantageously, a catalyst is used to synthesize the thermoplastic polyurethane.

[0140] TPUs are commercially available, for example, from Covestro (Desmopan series) and BASF (Elastollan series).

[0141] [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.

[0142] [Polysiloxane] According to a particular embodiment, the compatibilizer may be selected from polysiloxanes having the following structure: TIFF2025501595000005.tif34170A may be selected from a methyl group, an ethyl group, a propyl group, an isopropyl group or a pentyl group, and preferably A is a methyl group.

[0143] 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.

[0144] Examples of commercially available polysiloxanes include the MB 50 series from Dow Corning.

[0145] 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.

[0146] 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.

[0147] Preferably, the compositions of the present invention do not contain any of the following: -crosslinked polyurethane (PU) particles, and / or Thermoplastic SBS or SEBS.

[0148] The compositions according to the invention are thermoplastic, i.e. meltable.

[0149] 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.

[0150] Advantageously, the composition has a tan δ at 23 ° C. of less than or equal to 0.15, preferably less than or equal to 0.12, 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 0.11 to 0.15.

[0151] 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.

[0152] 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, preferably in a co-kneader, o at least one polyamide block polyether block copolymer in the molten state at 20% to 90% by weight, preferably 40% to 70% by weight, and o 10% to 80% by weight, preferably 30% to 60% by weight, of at least one crosslinked rubber powder, in particular from used tires, o 0 to 5% of additives, preferably 0.1% to 4%, particularly 1% to 2%, 0 to 40%, preferably 5 to 20%, particularly 10 to 15% of a compatibilizer; mixing, Optionally, forming the mixture into the form of granules, filaments or powder, and / or - Recovering the resulting composition. Includes.

[0153] The mixing step of the present method can be carried out by, inter alia, applying high shear, heat, or radiation to better disperse the rubber powder particles within the PEBA copolymer matrix and produce a homogenous mixture.

[0154] 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.

[0155] The articles or elements consisting of or including the above-mentioned compositions can in particular be manufactured by injection molding.

[0156] 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 at least a portion of said article made of a thermoplastic material comprising the composition of the present invention, optionally after separation; b) grinding the thermoplastic material to obtain particles; c) melting the particles obtained in the previous step 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; The present invention relates to a method comprising the steps of:

[0157] 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.

[0158] According to yet another aspect, the invention relates to granules, filaments or powder obtainable by the recycling method according to the claims.

[0159] 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.

[0160] The article is, for example, the sole of a shoe, in particular a sports shoe.

[0161] definition Throughout the description, the terms listed below have the following meanings:

[0162] 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 and diamines.

[0163] 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.

[0164] 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 PA L designation, 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 PA MN designation, M stands for the number of carbon atoms of the diamine and N for the number of carbon atoms of the dicarboxylic acid.

[0165] 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.

[0166] Examples of lactams include C6 to C18 lactams, particularly caprolactam, enantholactam, and lauryllactam.

[0167] 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.

[0168] 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).

[0169] 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.

[0170] The term "thermoplastic elastomer" refers to a polymer that contains flexible and rigid segments, for example in the form of a block copolymer, where the rigid segments disappear when the temperature is increased. Alternatively, it may be a mixture that combines the presence of a flexible elastomeric phase, crosslinked or not, dispersed in a rigid thermoplastic continuous phase. The mixture may in particular be a blend of a thermoplastic polymer and an elastomer.

[0171] 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.

[0172] It is further pointed out that, unless expressly stated otherwise, physical quantities are measured at normal conditions, in particular at 23° C. and in dry condition ("dry as molded").

[0173] The term "thermoplastic polymer" refers to a polymer that has the property of becoming soft when heated sufficiently and becoming hard again when cooled.

[0174] 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.

[0175] - The elongation at break is measured according to standard ISO 527-1A.

[0176] - 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.

[0177] 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.

[0178] Unless otherwise stated, percentages are expressed on a weight basis relative to the total weight of the composition.

[0179] Working Example The following examples illustrate the invention without limiting it.

[0180] 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 35. PEBA No. 2: PEBA copolymer comprising a rigid PA 12 block having a number average molar mass of 600 g / mol and a PTMG block having a number average molar mass of 2000 g / mol and a Shore D hardness of 25.

[0181] PEBA No. 3: PEBA copolymer comprising a rigid PA 11 block having a number average molar mass of 1000 g / mol and a PTMG block having a number average molar mass of 1000 g / mol and a Shore D hardness of 40. - 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 2The crosslinked rubber powder is derived from used tires and has a specific surface area of ​​about 1.0 μm / g. The D50 diameter of this powder is about 130 μm and the D90 is about 270 μm. TyreXol® MM30 is commercially available from TRS, 0.05 ml 2 The crosslinked rubber powder is derived from used tires and has a specific surface area of ​​about 1.0 μm / g. The D50 diameter of this powder is about 340 μm and the D90 is about 550 μm.

[0182] Various compositions were prepared, the content of each component in mass percentage is shown in Tables 1 and 2 below. [Table 1] TIFF2025501595000006.tif65163[Table 2] TIFF2025501595000007.tif65170

[0183] 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.

[0184] Compositions EI5 to EI15 were produced using a PR46 co-kneader (Bus). 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.

[0185] Composition EC1 is a crosslinked synthetic rubber sheet.

[0186] The composition was then dried under vacuum at 80° C. to achieve a moisture content of less than 0.04%.

[0187] Specimens 1A (according to standard ISO 527), 6 mm sheets, and 2 mm sheets were produced by injection molding using a Battenfeld BA800 CDC press and a textured mold. The following parameters were applied during injection: -Barrel temperature: 150℃ -Nozzle temperature: 170℃ -Mold temperature: 20℃. -Cycle time: 60 seconds.

[0188] 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 (-).

[0189] All of these evaluations were performed on dry (unconditioned) specimens.

[0190] The results are shown in Tables 3 and 4 below. [Table 3] TIFF2025501595000008.tif38170[Table 4] TIFF2025501595000009.tif38170

[0191] 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 polyamide block-polyether block copolymer; 10% to 80% by weight, preferably 30% to 60% by weight, of at least one crosslinked rubber powder, in particular from used tires, 0 to 5% by weight, preferably 0.1 to 4% by weight, in particular 1 to 2% by weight, of additives; Compatibilizer: 0 to 40% by weight, preferably 5 to 20% by weight, particularly 10 to 15% by weight A composition comprising:

2. The crosslinked rubber powder is 0.01 m ２ / g and 100m 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 an average particle size D50 between 2 μm and 500 μm, preferably between 50 μm and 300 μm.

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

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

6. 2. A composition according to claim 1, wherein the rubber of the crosslinked rubber crumb comprises 0 to 50% by weight, preferably 5 to 40% by weight, of a synthetic rubber or a mixture of synthetic rubbers.

7. 2. The composition of 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.

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

9. 2. The composition according to claim 1, wherein the crosslinked rubber powder comprises styrene butadiene rubber, preferably in a content of more than 5% by weight, more preferably in a content of more than 10% by weight.

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%, more preferentially from 10% to 40% of carbon black and / or silica.

12. 2. The composition according to claim 1, wherein the crosslinked rubber powder comprises less than 10%, preferably less than 5%, and very preferably less than 1% of fibrous material.

13. 2. A composition according to claim 1, wherein the crosslinked rubber powder advantageously comprises from 0.05% to 5% by weight, preferably from 0.1% to 2.5% by weight, of zinc oxide.

14. 10. The composition of claim 1, wherein the additive is selected from catalysts, antioxidants, heat stabilizers, UV stabilizers, light stabilizers, lubricants, flame retardants, nucleating agents, chain extenders, and dyes.

15. 2. The composition of claim 1, wherein at least one polyamide block-polyether block copolymer has a Shore hardness between 10D and 70D, preferably between 25D and 50D.

16. 2. The composition according to claim 1, wherein the polyamide blocks of the polyamide block-polyether block copolymer 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 copolymer are polyethylene glycol and / or polytetrahydrofuran blocks.

17. 17. A method for preparing a composition according to any one of claims 1 to 16, comprising: Preferably in an extruder, 20% to 90% by weight, preferably 40% to 70% by weight, of at least one polyamide block polyether block copolymer in the melt; 10% to 80% by weight, preferably 30% to 60% by weight, of at least one crosslinked rubber powder, in particular from used tires, 0 to 5%, preferably 0.1% to 4%, in particular 1% to 2% of additives, 0 to 40%, preferably 5 to 20%, particularly 10 to 15% of a compatibilizer mixing the Optionally, forming the mixture into the form of granules, filaments or powder; and / or - Recovering the resulting composition A method comprising:

18. 17. An article comprising at least one element comprising the composition of any one of claims 1 to 16, said article being preferably selected from footwear components such as shoe soles, ski pole parts, racket and golf club handles, goalkeeper gloves, treadmills, diving boots, underwater equipment such as mask 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.

19. 20. A method of manufacturing the article of claim 18, comprising: - providing a composition according to any one of claims 1 to 16; - injection molding said composition; A method comprising:

20. 20. A method for recycling an article according to claim 18, 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 16; 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 granules, filaments or powder; A method comprising:

21. Granules, filaments or powder obtainable according to the method for recycling according to claim 20.

22. 22. An article consisting of or comprising at least one element prepared from the granules, filaments or powder of claim 21.