Composition of Thermoplastic Polyurethane and Polyamide

Abstract

The present invention relates to compositions comprising at least one thermoplastic polyurethane and at least one polyamide comprising amine chain ends, the polyamide being the reaction product of one or more monomers selected from amino acids or aminocarboxylic acids, lactams, and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid. The present invention also relates to compositions obtained by the reaction of at least one thermoplastic polyurethane or thermoplastic polyurethane precursor and at least one polyamide comprising amine chain ends, to methods for preparing such compositions, and to articles made therefrom.

Description

[Technical field]

[0001] The present invention relates to a thermoplastic polyurethane and polyamide based composition and a method for preparing same. [Background technology]

[0002] Various polymer compositions are used, inter alia, in the field of sports equipment, such as soles or sole components, gloves, rackets or golf balls, or in particular personal protective equipment for sports practice (jackets, helmet inners, shells, etc.). Such applications require a set of specific physical properties that ensure resilience, low compressive or tensile strain, as well as the ability to withstand repeated impacts and return to the original shape. Polymer compositions are also used, for example, in the field of medical devices, such as catheters, or in other fields, such as watch bands, toys or for industrial applications, in particular production line conveyor belts.

[0003] Documents US 7,383,647 and EP 1871188 relate to footwear midsoles which may include one or more components made of thermoplastic polyurethanes (TPUs), polyester-TPUs, polyether-TPUs, polyester-polyether TPUs, polyvinyl chloride, polyesters, thermoplastic vinyl ethyl acetates, styrene-butadiene-styrene, block polyether amides, technical polyesters, TPU blends with natural and synthetic rubbers, or combinations thereof.

[0004] Document FR2831175 relates to a composition comprising a mixture of at least two thermoplastic polyurethanes and a compatibilizer in an amount of up to 15%, the compatibilizer being preferably a polyetheramide, polyesteramide or polyetheresteramide.

[0005] Document JP5393036 describes a thermoplastic resin composition comprising a thermoplastic resin and an antistatic agent containing a polyetheresteramide and a polyurethane-based thermoplastic elastomer.

[0006] Document JP5741139 describes a polyurethane resin composition comprising a thermoplastic polyurethane resin prepared by dry blending of the components, and a copolymer containing a polyamide block and a polyether block, the copolymer containing a polyamide block and the polyether block being formed by polymerizing a triblock polyetherdiamine, a dicarboxylic acid and a polyamide-forming monomer.

[0007] There is a practical need to provide a composition that has good tear strength, high elasticity, low density and satisfactory flexibility. Summary of the Invention

[0008] The present invention first provides at least one thermoplastic polyurethane, and - comprising at least one polyamide containing an amine chain end, Polyamide refers to a composition which is the reaction product of one or more monomers selected from amino acids or aminocarboxylic acids, lactams, and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid.

[0009] The present invention relates to - at least one thermoplastic polyurethane or thermoplastic polyurethane precursor, and - obtained by reaction of at least one polyamide containing an amine chain end, The polyamide also relates to a composition which is a reaction product of one or more monomers selected from amino acids or aminocarboxylic acids, lactams, and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid.

[0010] In an embodiment, at least a portion of the polyamide is covalently bonded to at least a portion of the thermoplastic polyurethane via urea functional groups, and the concentration of the urea functional groups in the composition is preferably from 0.001 meq / g to 0.1 meq / g, more preferably from 0.003 meq / g to 0.08 meq / g, more preferably from 0.005 meq / g to 0.05 meq / g.

[0011] In an embodiment, the polyamide has a concentration of NH2 amine functional groups from 0.02 meq / g to 2.0 meq / g, preferably from 0.04 meq / g to 1.5 meq / g.

[0012] In an embodiment, the composition has a tensile modulus at 23° C. of 1000 MPa or less, preferably 800 MPa or less.

[0013] In an embodiment, the composition further comprises at least one copolymer containing polyamide blocks and polyether blocks, preferably the polyamide blocks of the copolymer are selected from polyamide 6, polyamide 6.10, polyamide 6.12, polyamide 11, polyamide 10 and / or polyamide 12 blocks, and / or the polyether blocks of the copolymer are polyethylene glycol and / or polytetrahydrofuran blocks.

[0014] In an embodiment, the at least one polyamide comprising an amine chain end is present in an amount of 40% by weight or less, preferably 30% by weight or less, relative to the total weight of the composition.

[0015] In an embodiment, the composition comprises, based on the total weight of the composition: - 10% to 99% by weight, preferably 15% to 89% by weight, of at least one thermoplastic polyurethane, - from 1% to 40% by weight, preferably from 1% to 30% by weight, of at least one amine-terminated polyamide having chain ends, and It comprises at least one copolymer containing 0 to 89% by weight, preferably 10% to 70% by weight, of polyamide blocks and polyether blocks.

[0016] In an embodiment, the composition has a tan δ at 23° C. less than or equal to 0.18, preferably less than or equal to 0.16.

[0017] In an embodiment, the polyamide comprising amine chain ends has a number average molar mass of 1000 to 60000 g / mol, preferably 2000 to 40000 g / mol.

[0018] In embodiments, the thermoplastic polyurethane is a copolymer containing rigid and flexible blocks: the flexible blocks are selected from polyether blocks, polyester blocks, polycarbonate blocks and combinations thereof; preferably, the flexible blocks are selected from polyether blocks, polyester blocks and combinations thereof, and more preferentially are polytetrahydrofuran blocks, polypropylene glycol blocks and / or polyethylene glycol blocks; and / or the rigid block comprises units derived from diphenylmethane-4,4'-diisocyanate and / or hexamethylene-1,6-diisocyanate and preferably from at least one chain extender selected from 1,3-propanediol, 1,4-butanediol and / or 1,6-hexanediol;

[0019] In an embodiment, the polyamide comprising amine chain ends is selected from the group consisting of polyamide 11, polyamide 12, polyamide 10, polyamide 6, polyamide 6.10, polyamide 6.6, polyamide 10.10, polyamide 10.12, and combinations thereof.

[0020] The present invention relates to a method for preparing a composition, the method comprising the steps of: - mixing, preferably in an extruder, at least one polyamide comprising amine chain ends in the melt, at least one thermoplastic polyurethane in the melt and, optionally, at least one copolymer containing polyamide blocks and polyether blocks in the melt, wherein the polyamide comprising amine chain ends is a reaction product of one or more monomers chosen from amino acids or aminocarboxylic acids, lactams and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid; - optionally shaping the mixture in the form of granules or powder.

[0021] The present invention relates to a method for preparing a composition, the method comprising the steps of: - introducing into a reactor, preferably an extruder, at least one precursor of a thermoplastic polyurethane; - introducing into a reactor at least one polyamide comprising amine chain ends and optionally at least one copolymer comprising polyamide blocks and polyether blocks, the polyamide comprising amine chain ends being a reaction product of one or more monomers selected from amino acids or aminocarboxylic acids, lactams, and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid; - synthesizing a thermoplastic polyurethane in a reactor in the presence of a polyamide comprising amine chain ends to obtain a composition made of thermoplastic polyurethane and polyamide; - optionally comprising the step of compacting the composition in the form of granules or powder.

[0022] The present invention also relates to an article consisting of or comprising at least one element consisting of the composition described above, preferably selected from sports footwear soles, large or small balls, gloves, personal protective equipment, tie pads, automotive parts, structural parts, optical equipment parts, electrical and electronic equipment parts, watch bands, toys, medical equipment parts such as catheters, transmission or conveyor belts, gears and production line conveyor belts.

[0023] The present invention relates to a method for producing the above-mentioned article, comprising the steps of: - providing said composition; - a process comprising the step of injection molding said composition.

[0024] The present invention makes it possible to meet the demands mentioned above, more particularly by providing a composition having a relatively low density and exhibiting high elasticity, satisfactory flexibility and high tear strength and durability.

[0025] This is accomplished through the combination of a thermoplastic polyurethane (or TPU) and a polyamide (or PA) with amine (NH2) chain ends.

[0026] In one advantageous embodiment, the reaction takes place between at least a portion of the polyamide comprising amine chain ends and at least a portion of the thermoplastic polyurethane, more particularly between the amine functional groups of the polyamide and the urethane functional groups of the thermoplastic polyurethane or the isocyanate functional groups present in the precursors of the thermoplastic polyurethane. The reaction between at least a portion of the polyamide comprising amine chain ends and at least a portion of the thermoplastic polyurethane results in a better compatibility between these polymers, which results in and thus achieves improvements in the properties of the blend, particularly the properties mentioned above. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The invention is explained in more detail below and in a non-limiting manner in the description that follows.

[0028] The present invention relates to a composition comprising at least one thermoplastic polyurethane and at least one polyamide having an amine chain end. In this context, the terms "chain end" and "chain end" have the same meaning and may be used interchangeably.

[0029] Polyamide (PA) with amine chain ends The polyamide having amine chain ends can be a homopolyamide and / or a copolyamide.

[0030] The term "polyamide" means - amino acid or aminocarboxylic acid type monomers, preferably having from 6 to 14 carbon atoms, preferably alpha,omega-aminocarboxylic acids; - lactam type monomers, which preferably have from 3 to 18 carbon atoms in the main ring, which may be substituted; - monomers of the "diamine.diacid" type obtained by the reaction between an aliphatic diamine having preferably from 2 to 48 carbon atoms, more preferentially from 2 to 20 carbon atoms, and a dicarboxylic acid having preferably from 4 to 48 carbon atoms, more preferentially from 4 to 20 carbon atoms; and - means the product of polymerization of one or more monomers selected from a mixture of monomers containing different carbon numbers, in the case of mixtures between those of amino acid type and those of lactam type.

[0031] In this specification of polyamides, the term "monomer" should be interpreted as meaning "repeating unit". Indeed, a special case is when the repeating unit of a polyamide (PA) consists of a combination of a diacid and a diamine. This is considered to be a combination of a diamine and a diacid, i.e. a diamine.diacid pair (in equimolar amounts) that corresponds to a monomer. This is explained by the fact that individually, a diacid or a diamine is the only structural unit that is not sufficient to be polymerized by itself.

[0032] For the purposes of the present invention, a polyamide with amine chain ends consists exclusively of polyamide. In particular, it does not contain any blocks of another type, such as polyether blocks, polyester blocks, polysiloxane blocks, polyolefin blocks or polycarbonate blocks. More particularly, a polyamide with amine chain ends is not a copolymer containing polyamide blocks and polyether blocks. The composition according to the invention may contain polyamides with or without amine chain ends, including blocks other than polyamide blocks, with the proviso that it also includes polyamides with amine chain ends consisting exclusively of polyamide.

[0033] When the polyamide is a homopolyamide, it is the product of the polymerization of a single monomer. When the polyamide is a copolyamide, it is the product of the polymerization of at least two different monomers.

[0034] Advantageously, three types of polyamides may be used.

[0035] According to a first type, the polyamides result from the condensation of dicarboxylic acids, in particular those having from 4 to 48 carbon atoms, preferably those having from 4 to 20 carbon atoms and more preferentially those having from 6 to 18 carbon atoms, and aliphatic or aromatic diamines, in particular those having from 2 to 48 carbon atoms, preferably those having from 2 to 20 carbon atoms and more preferentially those having from 5 to 14 carbon atoms.

[0036] Examples of dicarboxylic acids may include 1,4-cyclohexanedicarboxylic acid, butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, terephthalic acid, and isophthalic acid, but may also include dimerized fatty acids.

[0037] Examples of diamines may include ethylenediamine, tetramethylenediamine, pentamethylenediamine, 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), para-aminodicyclohexylmethane (PACM), isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN) and piperazine (Pip).

[0038] Advantageously, the polyamides PA4.12, PA4.14, PA4.18, PA5.10, PA5.12, PA5.14, PA5.16, PA5.18, PA6.10, PA6.12, PA6.14, PA6.18, PA9.12, PA10.10, PA10.12, PA10.14 and PA10.18 are used. In the notation PAX.Y, as is conventional, X represents the number of carbon atoms derived from the diamine residue and Y represents the number of carbon atoms derived from the diacid residue.

[0039] According to a second type, the polyamides result from the condensation of one or more α,ω-aminocarboxylic acids and / or one or more lactams having 3 to 18 carbon atoms, preferably 6 to 14 carbon atoms, in the presence of a dicarboxylic acid having 2 to 48 carbon atoms, preferably 4 to 20 carbon atoms, or of a diamine. Examples of lactams may include caprolactam, oenantholactam and lauryllactam. Examples of α,ω-aminocarboxylic acids may include aminocaproic acid, 7-aminoheptanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.

[0040] Advantageously, the second type of polyamide is PA10 (polydecaneamide), PA11 (polyundecaneamide), PA12 (polydodecanamide) or PA6 (polycaprolactam). In the notation PAX, X represents the number of carbon atoms originating from an amino acid residue.

[0041] According to a third type, the polyamides result from the condensation of at least one α,ω-aminocarboxylic acid (or lactam), at least one diamine and at least one dicarboxylic acid.

[0042] In this case, the polyamide PA is - polycondensation of linear aliphatic or aromatic diamine(s) having X carbon atoms; - polycondensation of dicarboxylic acid(s) containing Y carbon atoms; - prepared by polycondensation of comonomer(s) {Z} selected from an equimolar mixture of lactams and α,ω-aminocarboxylic acids containing Z carbon atoms, and 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), - said comonomer(s) {Z} are introduced in a weight proportion ranging advantageously up to 50%, preferably up to 20% and even more advantageously up to 10%, relative to the total amount of polyamide-precursor monomers; - in the presence of a chain limiter selected from dicarboxylic acids.

[0043] 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(s).

[0044] According to a variant of this third type, the polyamide results from the condensation of at least two α,ω-aminocarboxylic acids containing 6 to 12 carbon atoms, or at least two lactams, or one lactam and one aminocarboxylic acid not having the same number of carbon atoms, optionally in the presence of a chain limiter. Examples of aliphatic α,ω-aminocarboxylic acids may include aminocaproic acid, 7-aminoheptanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. Examples of lactams may include caprolactam, oenantholactam and lauryllactam. Examples of aliphatic diamines may include pentamethylenediamine, hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine. Examples of alicyclic diacids may include 1,4-cyclohexanedicarboxylic acid. Examples of aliphatic diacids include butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, and dimerized fatty acids. These dimerized fatty acids preferably have a dimer content of at least 98%; they are preferably hydrogenated; they are, for example, the products sold under the brand name Pripol by Croda, or under the brand name Empol by BASF, or under the brand name Radiacid by Oleon, and polyoxyalkylene α,ω-diacids. Examples of aromatic diacids include terephthalic acid (T) and isophthalic acid (I). Examples of cycloaliphatic diamines include bis(4-aminocyclohexyl)methane (BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM) and isomers of 2,2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP), and para-aminodicyclohexylmethane (PACM).Other commonly used diamines can be isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN) and piperazine.

[0045] Examples of the third type of polyamide include: - PA6.6 / 6 (wherein 6.6 represents a hexamethylenediamine unit condensed with adipic acid and 6 represents a unit resulting from the condensation of caprolactam); Mention may be made of PA6.6 / 6.10 / 11 / 12, in which 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.

[0046] The notations PAX / Y, PAX / Y / Z etc. refer to copolyamides where X, Y, Z etc. represent homopolyamide units as defined above.

[0047] Advantageously, the polyamides used in the invention are the polyamides PA6, PA10, PA11, PA12, PA5.4, PA5.9, PA5.10, PA5.12, PA5.13, PA5.14, PA5.16, PA5.18, PA5.36, PA6.4, PA6.6, PA6.9, PA6.10, PA6.12, PA6.13, PA6.14, PA6.16, PA6.18, PA6.36, PA10.4, PA10.9, PA10.10, PA10.12, PA10.13, PA10.14, PA10.1 6, PA10.18, PA10.36, PA10.T, PA12.4, PA12.9, PA12.10, PA12.12, PA12.13, PA12.14, PA12.16, PA12.18, PA12.36, PA12.T, or mixtures or copolymers thereof; preferably comprising or consisting of the polyamide PA6, PA10, PA11, PA12, PA6.6, PA6.10, PA10.10, PA10.12, or mixtures or copolymers thereof.

[0048] Preferably, the amide bonds of the polyamide do not include tertiary amides (i.e. amides in which the amines are tertiary amines). More preferentially, all the amide bonds of the polyamide are secondary amides (i.e. amines of the amide bonds are secondary amines).

[0049] The polyamides containing amine chain ends advantageously have a number average molar mass of 1000 to 60 000 g / mol, preferably 2000 to 40 000 g / mol and very advantageously 2000 to 18 000 g / mol. In an embodiment, the polyamide with amine chain ends may have a number average molar mass of 1000 to 2000 g / mol; or 2000 to 3000 g / mol; or 3000 to 5000 g / mol; or 5000 to 10000 g / mol; or 10000 to 15000 g / mol; or 15000 to 20000 g / mol; or 20000 to 25000 g / mol; or 25000 to 30000 g / mol; or 30000 to 35000 g / mol; or 35000 to 40000 g / mol; or 40000 to 45000 g / mol; or 45000 to 50000 g / mol; or 50000 to 55000 g / mol; or 55000 to 60000 g / mol.

[0050] The number average molar mass is determined by the content of chain limiter, which is determined by the equation: M n =n モノマー ×MW 反復単位 / n 連鎖制限剤 +MW 連鎖制限剤 It can be calculated according to:

[0051] In this formula, n モノマー represents the number of moles of monomer, and n 連鎖制限剤 represents the excess moles of diacid limiting agent, and MW 反復単位 represents the molar mass of the repeating unit, and MW 連鎖制限剤 represents the excess molar mass of the diacid.

[0052] The number-average molar mass of the polyamide can be determined by gel permeation chromatography (GPC).

[0053] Preferably, at least 50% by weight (relative to the total weight of the polyamides containing amine chain ends) of the polyamides containing amine chain ends have a molar mass of less than or equal to 18000 g / mol, and more preferentially between 50% and 80% by weight of the polyamides containing amine chain ends have a molar mass of less than or equal to 18000 g / mol. These amounts of polyamide can be determined by GPC. These ranges make it possible to achieve better elasticity of the composition and better elongation at break.

[0054] The polyamide containing amine chain ends can be monofunctional (i.e., it contains a single amine chain end per molecule of PA) or difunctional (i.e., it contains two amine chain ends per molecule of PA); preferably it is monofunctional.

[0055] The polyamide preferably has a concentration of amine (NH2) functional groups of 0.02 meq / g to 2.0 meq / g, preferably 0.04 meq / g to 1.5 meq / g, more preferably 0.1 to 1.5 meq / g, more preferably 0.35 to 1.5 meq / g. In particular, the polyamide having amine chain ends has a concentration of 0.02 to 0.04 meq / g, or 0.04 to 0.06 meq / g, or 0.06 to 0.08 meq / g, or 0.08 to 0.1 meq / g, or 0.1 to 0.2 meq / g, or 0.2 to 0.3 meq / g, or 0.3 to 0.4 meq / g, or 0.4 to 0.5 meq / g, or 0.5 to 0.6 meq / g, or 0.6 to 0.7 meq / g, or 0.7 to 0.8 meq / g, or may have a concentration of NH2 functional groups of 0.8-0.9 meq / g, or 0.9-1.0 meq / g, or 1.0-1.1 meq / g, or 1.1-1.2 meq / g, or 1.2-1.3 meq / g, or 1.3-1.4 meq / g, or 1.4-1.5 meq / g, or 1.5-1.6 meq / g, or 1.6-1.7 meq / g, or 1.7-1.8 meq / g, or 1.8-1.9 meq / g, or 1.9-2.0 meq / g. The concentration of NH2 functional groups can be measured by potentiometric titration. This titration can be carried out, for example, in the following manner: the PA is first dissolved in m-cresol at 80 °C, and then the terminal NH2 functional groups are titrated with a perchloric acid solution.

[0056] Polyamides containing amine chain ends may have a concentration of COOH functional groups from 0.002 meq / g to 0.2 meq / g, preferably from 0.005 meq / g to 0.1 meq / g, more preferably from 0.01 meq / g to 0.08 meq / g. In particular, the polyamide according to the invention may have a concentration of COOH functional groups 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 concentration of COOH functional groups can be determined by potentiometric titration analysis. The measurement protocol is described in detail in the article "Synthesis and characterization of poly(copolyethers-block-polyamides) - II. Characterization and properties of the multiblock copolymers", Marechal et al., Polymer, Vol. 41, 2000, pp. 3561-3580.

[0057] The above concentrations (of amine and COOH functional groups) correspond to the concentrations of polyamides containing amine chain ends incorporated throughout (i.e., if the composition contains several polyamides containing amine chain ends, all of these polyamides are considered).

[0058] Polyamides containing amine chain ends can be prepared by condensation of polyamide precursors (i.e. of the monomers mentioned above). Advantageously, the addition of a diamine chain limiter makes it possible to increase the concentration of amine chain ends in the polyamide. During the synthesis of the polyamide, the molar ratio of NH2 amine functional groups to COOH functional groups of all the monomers introduced into the reactor makes it possible to determine the concentration of amine chain ends in the polyamide.

[0059] The molar ratio of NH2 amine functions to COOH functions is advantageously between 0.7 and 1.3, preferentially between 0.85 and 1.25.

[0060] The polyamide containing amine chain ends is advantageously semi-crystalline. It preferably has a melting enthalpy of more than 5 J / g. The melting enthalpy can be measured by differential scanning calorimetry (DSC) analysis according to standard ISO11357-3 Plastics - Differential scanning calorimetry (DSC) Part 3.

[0061] Thermoplastic Polyurethane (TPU) The thermoplastic polyurethanes according to the present invention are copolymers of rigid and flexible blocks.

[0062] Generally, in the present text, the term "rigid block" is understood to mean a block having a melting point. The presence of a melting point can be determined by differential scanning calorimetry according to the standard ISO11357-3 Plastics - Differential scanning calorimetry (DSC) Part 3. The term "flexible block" means a block having a glass transition temperature (Tg) below 0°C. The glass transition temperature can be determined by differential scanning calorimetry according to the standard ISO11357-2 Plastics - Differential scanning calorimetry (DSC) Part 2.

[0063] Thermoplastic polyurethanes result from the reaction of at least one polyisocyanate with at least one isocyanate-reactive compound, more preferentially a polyol, preferably having two isocyanate-reactive functional groups, and optionally with a chain extender, optionally in the presence of a catalyst. The rigid blocks of the TPU are blocks consisting of units derived from polyisocyanates and chain extenders, whereas the flexible blocks mainly comprise units derived from isocyanate-reactive compounds, preferably polyols, with a molar mass between 0.5 and 100 Kg / mol.

[0064] The polyisocyanates may be aliphatic, cycloaliphatic, araliphatic and / or aromatic. Preferably, the polyisocyanates are diisocyanates.

[0065] 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, pentamethylene-1,5-diisocyanate, butylene-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane. Hexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), paraphenylene-2,4-diisocyanate (PPDI), tetramethylxylene-2,4-diisocyanate (TMXDI), dicyclohexylmethane-4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12 The diisocyanate is selected from the group consisting of cyclohexane-1,4-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate and / or 1-methylcyclohexane-2,6-diisocyanate, diphenylmethane-2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), naphthylene-1,5-diisocyanate (NDI), toluene-2,4- and / or 2,6-diisocyanate (TDI), diphenylmethane diisocyanate, dimethyldiphenyl-3,3'-diisocyanate, diphenylethane-1,2-diisocyanate, phenylene diisocyanate, methylenebis(4-cyclohexylisocyanate) (HMDI) and mixtures thereof.

[0066] 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.

[0067] Even more preferably, the polyisocyanate is 4,4'-MDI (diphenylmethane-4,4'-diisocyanate), 1,6-HDI (hexamethylene-1,6-diisocyanate) or a mixture thereof.

[0068] The isocyanate-reactive compound(s) preferably have an average functionality between 1.8 and 3, more preferably between 1.8 and 2.6, more preferably between 1.8 and 2.2. The average functionality of the isocyanate-reactive compound(s) corresponds to the number of isocyanate-reactive functional groups of the molecule, theoretically calculated per molecule from a given amount of compound. Preferably, the isocyanate-reactive compound has, according to a statistical average, a number of Zerewitinoff active hydrogens within the above range.

[0069] Preferably, the isocyanate-reactive compound (preferably a polyol) has a number average molar mass of 500 to 100000 g / mol. The isocyanate-reactive compound may have a number average molar mass of 500 to 8000 g / mol, more preferably 700 to 6000 g / mol, more particularly 800 to 4000 g / mol. In an embodiment, the isocyanate-reactive compound has a molecular weight of 500 to 600 g / mol, or 600 to 700 g / mol, or 700 to 800 g / mol, or 800 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 800 g / mol, or 800 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 800 to 9000 g / mol, or 900 to 1000 g / mol, or 1000 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 6 000 g / mol, or 7000-8000 g / mol, or 8000-10000 g / mol, or 10000-15000 g / mol, or 15000-20000 g / mol, or 20000-30000 g / mol, or 30000-40000 g / mol, or 40000-50000 g / mol, or 50000-60000 g / mol, or 60000-70000 g / mol, or 70000-80000 g / mol, or 80000-100000 g / mol. The number average molar mass can be determined by GPC, preferably according to the standard ISO 16014-1:2012.

[0070] 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 reactive hydroxyl group, more preferentially several hydroxyl groups. Thus, particularly advantageously, the isocyanate-reactive compound comprises or consists of a polyol.

[0071] 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. More 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).

[0072] The polyester polyols may 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. More specifically, the copolyesters may be based on adipic acid and a mixture of 1,2-ethanediol and 1,4-butanediol, or the copolyesters may be based on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof, and polytetrahydrofuran (tetramethylene glycol) or the copolyesters may be mixtures of these copolyesters.

[0073] Polyether diols (i.e. aliphatic α,ω-dihydroxyl polyoxyalkylene blocks) are preferably used as polyether polyols. Preferably, the polyether polyols are polyether diols based on ethylene oxide, propylene oxide and / or butylene oxide, block copolymers based on ethylene oxide and propylene oxide, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetrahydrofuran, polybutanediol or mixtures thereof. The polyether polyols are preferably polytetrahydrofuran (the flexible blocks of the thermoplastic polyurethane are therefore polytetrahydrofuran blocks), and / or polypropylene glycol (the flexible blocks of the thermoplastic polyurethane are therefore polypropylene glycol blocks), and / or polyethylene glycol (the flexible blocks of the thermoplastic polyurethane are therefore polyethylene glycol blocks), 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 the reaction product of ethylene oxide and propylene oxide; the molar ratio of ethylene oxide to propylene oxide is preferably between 0.01 and 100, more preferentially between 0.1 and 9, more preferentially between 0.25 and 4, more preferentially between 0.4 and 2.5, more preferentially between 0.6 and 1.5, more preferentially 1.

[0074] The polysiloxane diols 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 the standard ISO 16014-1:2012. Advantageously, the polysiloxane diol has the formula (I): HO-[RO] n -R-Si(R')2-[O-Si(R')2] m -O-Si(R')2-R-[OR] p -OH(I) [wherein R is preferably a C2-C4 alkylene, R' is preferably a C1-C4 alkyl, n, m and p each independently preferably represent an integer between 0 and 50, m being more preferably 1 to 50, even more preferentially 2 to 50]. Preferably, the polysiloxane has the following formula (II): TIFF2024517425000001.tif18170 [wherein Me is a methyl group] or the following formula (III): I have TIFF2024517425000002.tif15170.

[0075] The polyalkylene diols which can be used in the present invention are preferably butadiene-based.

[0076] The polycarbonate diols that can be used in the present invention are preferably aliphatic polycarbonate diols. The polycarbonate diols are preferably based on alkanediols. Preferably, they are strictly bicyclic. The preferred polycarbonate diols according to the present invention are based on butanediol, pentanediol and / or hexanediol, in particular on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane-(1,5)-diol, or mixtures thereof, and more preferentially on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or mixtures thereof. In particular, the polycarbonate diols can be based on butanediol and hexanediol, or on pentanediol and hexanediol, or on hexanediol, or a mixture of two or more of these polycarbonate diols. The polycarbonate diols advantageously have a number average molar mass between 500 and 4000 g / mol, preferably between 650 and 3500 g / mol and more preferentially between 800 and 3000 g / mol. The number average molar mass can be determined by GPC, preferably according to the standard ISO 16014-1:2012.

[0077] One or more polyols may be used as the isocyanate-reactive compound.

[0078] Particularly preferably, the flexible blocks of TPU are blocks of polytetrahydrofuran, polypropylene glycol and / or polyethylene glycol.

[0079] Preferably, a chain extender is used in addition to the isocyanate and the isocyanate-reactive compound in preparing the thermoplastic polyurethane.

[0080] The chain extender is aliphatic, araliphatic, aromatic and / or cycloaliphatic. It advantageously has a number-average molar mass of 50 to 499 g / mol. The number-average molar mass can be determined by GPC, preferably according to standard ISO 16014-1:2012. The chain extender preferably has two isocyanate-reactive groups (also called "functional groups"). It is possible to use a single chain extender or a mixture of at least two chain extenders.

[0081] The chain extender is preferably difunctional. Examples of chain extenders are diamines and alkanediols having 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 it is selected from 1,3-propanediol, 1,4-butanediol and / or 1,6-hexanediol. Even more preferentially, the chain extender is a mixture of 1,4-butanediol and 1,6-hexanediol, more preferentially in a molar ratio of 6:1 to 10:1.

[0082] Advantageously, a catalyst is used to synthesize the thermoplastic polyurethane, which makes it possible to accelerate the reaction between the NCO groups of the polyisocyanate and the hydroxyl groups of the isocyanate-reactive compounds, preferably with the chain extenders, if present.

[0083] The catalyst is preferably a tertiary amine, more preferentially selected from triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol and / or diazabicyclo-(2,2,2)-octane. Alternatively or in addition, the catalyst is an organometallic compound, such as a titanate ester, an iron compound, preferably ferric acetylacetonate, a tin compound, preferably a carboxylic acid, more preferentially tin diacetate, tin dioctoate, tin dilaurate or a dialkyltin salt, preferably dibutyltin diacetate and / or dibutyltin dilaurate, a bismuth carboxylate, preferably bismuth decanoate or a mixture thereof.

[0084] More preferably, the catalyst is selected from the group consisting of tin dioctate, bismuth decanoate, titanate esters and mixtures thereof. More preferably, the catalyst is tin dioctate.

[0085] During the preparation of thermoplastic polyurethanes, the molar ratio of isocyanate-reactive compounds and chain extenders can be adjusted to vary the hardness and melt flow index of the TPU. Specifically, as the ratio of chain extenders increases, the hardness and melt viscosity of the TPU increases, while the melt flow index of the TPU decreases. In the production of flexible TPUs, preferably, TPUs with a Shore A hardness of less than 95, more preferentially 75-95, isocyanate-reactive compounds and chain extenders can be used in a molar ratio of 1:1-1:5, preferably 1:1.5-1:4.5, so that the mixture of isocyanate-reactive compounds and chain extenders preferably has a hydroxyl equivalent weight of more than 200, more particularly 230-650, even more preferentially 230-500. For harder TPU products, preferably TPU with a Shore A hardness of more than 98, preferably Shore D hardness of 55-75, isocyanate-reactive compound and chain extender can be used in a molar ratio of 1:5.5 to 1:15, preferably 1:6 to 1:12, so that preferably the mixture of isocyanate-reactive compound and chain extender has a hydroxyl equivalent weight of 110 to 200, more preferentially 120 to 180.

[0086] Advantageously, to prepare the TPU, the polyisocyanate, the isocyanate-reactive compound and preferably the chain extender are reacted, preferably in the presence of a catalyst in an amount such that the total equivalent ratio of the NCO groups of the polyisocyanate to the hydroxyl groups of the isocyanate-reactive compound and the chain extender is between 0.95:1 and 1.10:1, preferably between 0.98:1 and 1.08:1, more preferably between 1:1 and 1.05:1. The catalyst is advantageously present in an amount of between 0.0001 and 0.1 parts by weight per 100 parts by weight of the TPU synthesis reagents.

[0087] The TPU according to the invention preferably has a weight average molecular weight of at least 10000 g / mol, preferably at least 40000 g / mol, more preferentially at least 60000 g / mol. Preferably, the weight average molecular weight of the TPU is at most 80000 g / mol. The weight average molecular weight can be determined by gel permeation chromatography (GPC).

[0088] Advantageously, the TPU is semi-crystalline. Its melting temperature Tm is preferably between 100° C. and 230° C., more preferably between 120° C. and 200° C. The melting temperature can be measured according to the standard ISO 11357-3 Plastics - Differential scanning calorimetry (DSC) Part 3.

[0089] Advantageously, the TPU may be a recycled TPU and / or a partially or fully bio-based TPU.

[0090] Preferably, the TPU has a Shore D hardness of less than or equal to 75, more preferentially less than or equal to 65. In particular, the TPU used in the present invention may have a hardness of 65 Shore A to 70 Shore D, preferably 75 Shore A to 60 Shore D. The hardness measurement may be carried out according to the standard ISO 7619-1.

[0091] 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 an embodiment, the TPU according to the invention has a concentration of OH functional groups from 0.002 to 0.005 meq / g, or from 0.005 to 0.01 meq / g, or from 0.01 to 0.02 meq / g, or from 0.02 to 0.04 meq / g, or from 0.04 to 0.06 meq / g, or from 0.06 to 0.08 meq / g, or from 0.08 to 0.1 meq / g, or from 0.1 to 0.2 meq / g, or from 0.2 to 0.3 meq / g, or from 0.3 to 0.4 meq / g, or from 0.4 to 0.5 meq / g, or from 0.5 to 0.6 meq / g. The concentration of OH functional groups can be determined by NMR according to the conditions described in the following article: "Reactivity of isocyanates with urethanes: Conditions for allophanate formation", Lapprand et al., Polymer Degradation and Stability, Vol. 90, No. 2, 2005, pp. 363-373.

[0092] Copolymers containing polyamide blocks and polyether blocks (PEBA) The composition according to the invention may also comprise copolymers containing polyamide blocks and polyether blocks.

[0093] The presence of a copolymer containing polyamide blocks and polyether blocks in the composition makes it possible to reduce the density of the composition.

[0094] PEBA is produced by the polycondensation of polyamide blocks (rigid or hard blocks) bearing reactive ends and polyether blocks (flexible or soft blocks) bearing reactive ends, e.g., 1) a polyamide block having diamine chain ends and a polyoxyalkylene block having dicarboxyl chain ends; 2) polyamide blocks carrying dicarboxyl chain ends and polyoxyalkylene blocks carrying diamine chain ends, which are obtainable, for example, by cyanoethylation and hydrogenation of aliphatic α,ω-dihydroxyl polyoxyalkylene blocks known as polyether diols; 3) Resulting from the polycondensation of polyamide blocks carrying dicarboxyl chain ends with polyether diols, the resulting product being, in this particular case, a polyetheresteramide.

[0095] Polyamide blocks bearing dicarboxyl chain ends result, for example, from the condensation of polyamide precursors in the presence of a dicarboxylic acid chain limiter. Polyamide blocks bearing diamine chain ends result, for example, from the condensation of polyamide precursors in the presence of a diamine chain limiter.

[0096] The polyamide blocks (i.e. the nature of the polyamide) of the PEBA according to the invention may be, for example, the polyamides described in the preceding sections relating to polyamides containing amine chain ends (whether the polyamide blocks of the PEBA originate from polyamide blocks bearing diamine chain ends or bearing dicarboxylic acid chain ends). In particular, three types of polyamide blocks may advantageously be used, corresponding to the three types of polyamides described above.

[0097] More specifically, the polyamide block copolymers used in the present invention are polyamides PA6, PA10, PA11, PA12, PA5.4, PA5.9, PA5.10, PA5.12, PA5.13, PA5.14, PA5.16, PA5.18, PA5.36, PA6.4, PA6.6, PA6.9, PA6.10, PA6.12, PA6.13, PA6.14, PA6.16, PA6.18, PA6.36 , PA10.4, PA10.9, PA10.10, PA10.12, PA10.13, PA10.14, PA10.16, PA10.18, PA10.36, PA10.T, PA12.4, PA12.9, PA12.10, PA12.12, PA12.13, PA12.14, PA12.16, PA12.18, PA12.36, PA12.T, or blocks of mixtures or copolymers thereof.

[0098] Preferably, the polyamide blocks of the copolymer comprise blocks of polyamide PA6, PA10, PA11, PA12, PA6.10, PA6.12, PA10.10, PA10.12, or mixtures or copolymers thereof, more preferentially blocks of polyamide PA11, PA12, PA6, PA6.12, or mixtures or copolymers thereof.

[0099] The polyether blocks consist of alkylene oxide units.

[0100] The polyether blocks may in particular be PEG (polyethylene glycol) blocks, i.e. blocks made up of ethylene oxide units, and / or PPG (propylene glycol) blocks, i.e. blocks made up of propylene oxide units, and / or PO3G (polytrimethylene glycol) blocks, i.e. blocks made up of polytrimethylene glycol ether units, and / or PTMG (polytetramethylene glycol) blocks, i.e. blocks made up of tetramethylene glycol units, also known as polytetrahydrofuran. Copolymers may contain several types of polyether in their chains, copolyethers being optionally in block or random form.

[0101] Use may also be made of blocks obtained by oxyethylation of bisphenols, for example bisphenol A. The latter products are described in detail in document EP 613919.

[0102] The polyether blocks may also be comprised of ethoxylated primary amines. Examples of ethoxylated primary amines include those of the formula: TIFF2024517425000003.tif31170, in which m and n are integers between 1 and 20, and x is an integer between 8 and 18. These products are commercially available, for example, from CECA under the brand name Noramox® and from Clariant under the brand name Genamin®.

[0103] The polyether flexible block may comprise a polyoxyalkylene block carrying an NH2 chain end, such a block being obtainable by cyanoacetylation of an α,ω-dihydroxylated aliphatic polyoxyalkylene block, called polyether diol. More particularly, the commercial products Jeffamine or Elastamine can be used (for example Jeffamine® D400, D2000, ED2003 or XTJ542, which are commercial products from Huntsman and are also described in documents JP2004 / 346274, JP2004 / 352794 and EP1482011).

[0104] The polyether diol blocks are used in unmodified form and copolycondensed with the carboxyl-terminated rigid blocks, or are aminated for conversion to polyether diamines and condensation with the carboxyl-terminated rigid blocks.

[0105] A general method for the two-step preparation of PEBA copolymers having ester bonds between the PA and PE blocks is known and is described, for example, in document FR 2846332. A general method for the preparation of PEBA copolymers carrying amide bonds between the PA and PE blocks is known and is described, for example, in EP 148 2011. The polyether block can also be mixed with a polyamide precursor and a diacid chain limiter to prepare a polymer comprising polyamide blocks and polyether blocks with randomly distributed units (one-step method).

[0106] It goes without saying that the designation PEBA in this specification of the present invention relates not only to the products Pebax® sold by Arkema, Vestamid® sold by Evonik® (Evonik®), and Grilamid® sold by EMS, but also to the products Pelestat® type PEBA sold by Sanyo, or any other PEBA from other suppliers.

[0107] The present invention covers copolymers comprising a single polyamide block and a single flexible block, but also copolymers comprising three, four (or even more) different blocks selected from those described herein, with the proviso that these blocks comprise at least one polyamide block and one polyether block.

[0108] For example, the copolymer may be a segmented block copolymer (or "triblock" copolymer) containing three different types of blocks, resulting from the condensation of several of the above blocks. The triblock may be, for example, a copolymer containing a polyamide block, a polyester block and a polyether block, or a copolymer containing a polyamide block and two different polyether blocks, such as a PEG block and a PTMG block. The triblock is preferably a copolyetheresteramide.

[0109] Particularly preferred PEBA copolymers in the context of the present invention are copolymers comprising blocks of: PA10 and PEG; PA10 and PTMG; PA11 and PEG; PA11 and PTMG; PA12 and PEG; PA12 and PTMG; PA6.10 and PEG; PA6.10 and PTMG; PA6 and PEG; PA6 and PTMG; PA6.12 and PEG; PA6.12 and PTMG.

[0110] The number average molar mass of the polyamide blocks in the PEBA copolymer is preferably 400 to 20000 g / mol, more preferentially 500 to 10000 g / mol. In one embodiment, 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 70 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.

[0111] The number average molar mass of the polyether blocks is preferably between 100 and 6000 g / mol, more preferentially between 200 and 3000 g / mol. In one embodiment, the number average molar mass of the polyether blocks is between 100 and 200 g / mol, or between 200 and 500 g / mol, or between 500 and 800 g / mol, or between 800 and 1000 g / mol, or between 1000 and 1500 g / mol, or between 1500 and 2000 g / mol, or between 2000 and 2500 g / mol, or between 2500 and 3000 g / mol, or between 3000 and 3500 g / mol, or between 3500 and 4000 g / mol, or between 4000 and 4500 g / mol, or between 4500 and 5000 g / mol, or between 5000 and 5500 g / mol, or between 5500 and 6000 g / mol.

[0112] The number average molar mass is calculated using the equation: M n =n モノマー ×MW 反復単位 / n 連鎖制限剤 +MW 連鎖制限剤 It can be calculated according to:

[0113] The number-average molar masses of the polyamide blocks and of the polyether blocks can be determined by gel permeation chromatography (GPC) prior to copolymerization of the blocks.

[0114] 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 even 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 to 5, or 5 to 5.5, or 5.5 to 6, or 6 to 6.5, or 6.5 to 7, or 7 to 7.5, or 7.5 to 8, or 8 to 8.5, or 8.5 to 9, or 9 to 9.5, or 9.5 to 10, or 10 to 11, or 11 to 12, or 12 to 13, or 13 to 14, or 14 to 15, or 15 to 16, or 16 to 17, or 17 to 18, or 18 to 19, or 19 to 20.

[0115] Advantageously, the copolymers containing polyamide blocks and polyether blocks have a Shore D hardness of greater than or equal to 30. Preferably, the copolymers used in the invention have an instantaneous hardness of 65 Shore A to 80 Shore D, more preferably 75 Shore A to 65 Shore D and even more preferentially 80 Shore A to 55 Shore D. The hardness measurement can be carried out according to the standard ISO 7619-1.

[0116] The PEBA according to the present invention may have a concentration of OH functional groups 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, and / or a concentration of COOH functional groups 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 according to the present invention has a molecular weight of from 0.002 meq / g to 0.005 meq / g, or from 0.005 to 0.01 meq / g, or from 0.01 to 0.02 meq / g, or from 0.02 to 0.03 meq / g, or from 0.03 to 0.04 meq / g, or from 0.04 to 0.05 meq / g, or from 0.05 to 0.06 meq / g, or from 0.06 to 0.07 meq / g, or from 0.07 to 0.08 meq / g, or from 0.08 to 0.09 meq / g, or from 0.09 to 0.1 meq / g, or from 0.1 to 0.15 meq / g, or from 0.15 to 0.2 meq / g, and / or It may have a concentration of COOH functional groups of 0.002-0.005 meq / g, or a concentration of OH functional groups of 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 concentration of COOH functional groups may be determined by potentiometric titration analysis and the concentration of OH functional groups may be determined by proton NMR. The measurement protocol is described in detail in the article "Synthesis and characterization of poly(copolyethers-block-polyamides) - II. Characterization and properties of the multiblock copolymers", Marechal et al., Polymer, Vol. 41, 2000, pp. 3561-3580.

[0117] The PEBA according to the present invention may have a concentration of NH2 functional groups from 0.01 meq / g to 1 meq / g, preferably from 0.02 meq / g to 0.4 meq / g. The PEBA may have a concentration of NH2 functional groups from 0.01 to 0.015 meq / g, or from 0.015 to 0.02 meq / g, or from 0.02 to 0.025 meq / g, or from 0.025 to 0.03 meq / g, or from 0.03 to 0.035 meq / g, or from 0.035 to 0.04 meq / g, or from 0.04 to 0.045 meq / g, or from 0.045 to 0.05 meq / g, or from 0.05 to 0.06 meq / g, or from 0.06 to 0.07 meq / g, or from 0.07 to 0. The PEBA may have a concentration of NH2 functional groups of 0.08 meq / g, or 0.08-0.09 meq / g, or 0.09-0.1 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, or 0.6-0.7 meq / g, or 0.7-0.8 meq / g, or 0.8-0.9 meq / g, or 0.9-1 meq / g. The concentration of NH2 functional groups can be measured by potentiometric titration. This titration can be carried out, for example, in the following manner: the PEBA is first dissolved in m-cresol at 80° C., and then the terminal NH2 functional groups are titrated with a perchloric acid solution.

[0118] TPU and PA Compositions The composition according to the invention is a blend comprising at least one PA and at least one TPU, and optionally at least one PEBA. The term "blend" is understood to mean a homogeneous mixture (a macroscopically homogeneous mixture, i.e. a mixture that is uniform to the naked eye).

[0119] Preferably, the amount of polyamide containing amine chain ends in the composition is no more than 40% by weight, preferably no more than 30% by weight.

[0120] More preferentially, the composition according to the invention comprises, relative to the total weight of the polyamide containing amine chain ends and the thermoplastic polyurethane, from 1% to 40% by weight of at least one polyamide containing amine chain ends and from 60% to 99% by weight of at least one thermoplastic polyurethane, preferably from 1% to 30% by weight of at least one polyamide containing amine chain ends and from 70% to 99% by weight of at least one thermoplastic polyurethane, preferably from 1% to 25% by weight of at least one polyamide containing amine chain ends and from 75% to 99% by weight of at least one thermoplastic polyurethane, more preferentially from 1.5% to 25% by weight of at least one polyamide with amine chain ends and from 75% to 98.5% by weight of at least one thermoplastic polyurethane, even more preferentially from 2% to 20% by weight of at least one polyamide containing amine chain ends and from 80% to 98% by weight of at least one thermoplastic polyurethane. When the polyamide and the TPU are present in the above ranges, the elasticity of the composition is improved.In an embodiment, the composition comprises, based on the combined weight of the polyamide with amine chain ends and the thermoplastic polyurethane, 1% to 5% by weight of at least one polyamide with amine chain ends and 95% to 99% by weight of at least one thermoplastic polyurethane, or 5% to 10% by weight of at least one polyamide with amine chain ends and 90% to 95% by weight of at least one thermoplastic polyurethane, or 10% to 15% by weight of at least one polyamide with amine chain ends and 85% to 90% by weight of at least one thermoplastic polyurethane, or 15% to 20% by weight of at least one polyamide with amine chain ends and 80% to 85% by weight of at least one thermoplastic polyurethane, or 20% to 25% by weight of at least one polyamide containing amine chain ends and 75% to 80% by weight of at least one thermoplastic polyurethane, or 25% to 30% by weight of at least one polyamide containing amine chain ends and 70% to 75% by weight of at least one thermoplastic polyurethane, or 30% to 35% by weight of at least one polyamide containing amine chain ends and 65% to 70% by weight of at least one thermoplastic polyurethane, or 35% to 40% by weight of at least one polyamide containing amine chain ends and 60% to 65% by weight of at least one thermoplastic polyurethane.

[0121] The composition according to the invention advantageously comprises from 1% to 40% by weight of at least one polyamide comprising amine chain ends and from 10% to 99% by weight of at least one thermoplastic polyurethane, preferably from 1% to 30% by weight of at least one polyamide comprising amine chain ends and from 15% to 89% by weight of at least one thermoplastic polyurethane, more preferably from 1% to 25% by weight of at least one polyamide comprising amine chain ends and from 15% to 89% by weight of at least one thermoplastic polyurethane. The composition may comprise from 1% to 5% by weight, or from 5% to 10% by weight, or from 10% to 15% by weight, or from 15% to 20% by weight, or from 20% to 25% by weight, or from 25% to 30% by weight, or from 30% to 35% by weight, or from 35% to 40% by weight of at least one polyamide comprising amine chain ends, relative to the total weight of the composition. The composition may comprise from 10% to 20% by weight, or from 20% to 30% by weight, or from 30% to 40% by weight, or from 40% to 50% by weight, or from 50% to 60% by weight, or from 60% to 70% by weight, or from 70% to 80% by weight, or from 80% to 90% by weight, or from 90% to 99% by weight, based on the total weight of the composition, of at least one thermoplastic polyurethane.

[0122] The composition may also contain at least one PEBA, advantageously in an amount of 0 to 89% by weight, more preferentially 10% to 70% by weight, relative to the total weight of the composition. In particular, the composition may contain 0 to 10% by weight, or 10% to 20% by weight, or 20% to 30% by weight, or 30% to 40% by weight, or 40% to 50% by weight, or 50% to 60% by weight, or 60% to 70% by weight, or 70% to 80% by weight, or 80% to 89% by weight, relative to the total weight of the composition. The composition may not contain a copolymer containing a polyamide block and a polyether block. The amount of PEBA in the above ranges may be combined with any amount of polyamide containing amine chain ends in the ranges mentioned above, and / or any amount of thermoplastic polyurethane in the ranges.

[0123] The molar ratio of urethane functional groups to NH2 amine functional groups of the assembly consisting of at least one polyamide containing amine chain ends and at least one thermoplastic polyurethane in the composition according to the invention can be between 15 and 350, preferably between 25 and 250, and even more preferably between 40 and 200. The concentration of amine and urethane functional groups can be determined by NMR according to the conditions described in the following article: "Reactivity of isocyanates with urethanes: Conditions for allophanate formation", Lapprand et al., Polymer Degradation and Stability, Vol. 90, No. 2, 2005, pp. 363-373.

[0124] The composition according to the invention may consist of at least one polyamide comprising amine chain ends, at least one thermoplastic polyurethane, and optionally at least one copolymer containing polyamide blocks and polyether blocks.

[0125] Alternatively, the composition may comprise one or more additives, preferably chosen from impact modifiers, functional or non-functional polyolefins, copolyetheresters, ethylene / vinyl acetate copolymers, ethylene / acrylate copolymers, ethylene / alkyl(meth)acrylate copolymers, copolymers containing ethylene and styrene, polyorganosiloxanes, plasticizers, nucleating agents, lubricants, mould release agents, dyes, pigments, organic or inorganic fillers, reinforcing agents, flame retardants, UV absorbers, optical brighteners, light stabilizers, antioxidants and mixtures thereof. Advantageously, the additives are present in an amount of 0.1% to 20% by weight, preferably 0.2% to 10% by weight, relative to the total weight of the composition.

[0126] The composition according to the invention preferably has a tensile modulus of less than or equal to 1000 MPa at 23° C. More preferably, the composition according to the invention has a tensile modulus of less than or equal to 800 MPa, and more preferentially less than or equal to 500 MPa, at 23° C. The tensile modulus of the composition can be determined according to standard ISO 527-1A. The tensile modulus of the composition at 23°C may be from 20 to 40 MPa, or from 40 to 60 MPa, or from 60 to 80 MPa, or from 80 to 100 MPa, or from 100 to 150 MPa, or from 150 to 200 MPa, or from 200 to 250 MPa, or from 250 to 300 MPa, or from 300 to 350 MPa, or from 350 to 400 MPa, or from 400 to 450 MPa, or from 450 to 500 MPa, or from 500 to 550 MPa, or from 550 to 600 MPa, or from 600 to 700 MPa, or from 700 to 800 MPa, or from 800 to 900 MPa, or from 900 to 1000 MPa.

[0127] Preferably, the weight of the total flexible block (i.e. the flexible block of thermoplastic polyurethane and, if present, PEBA) is between 20% and 90%, more preferentially between 40% and 80%, even more preferentially between 50% and 75%, based on the total weight of the TPU and, if present, PEBA. The weight of the total flexible block can be determined by nuclear magnetic resonance (NMR).

[0128] Advantageously, the composition has a tan δ at 23 ° C. less than or equal to 0.18, preferably less than or equal to 0.16, more preferably less than or equal to 0.14. Tan δ (or loss factor) corresponds to the ratio of the loss modulus E ″ to the elastic modulus E ′ measured by dynamic mechanical analysis (DMA) at a temperature of 23 ° C. It can be measured according to standard ISO 6721 from 2019, the measurements being carried out at a tensile strain of 0.1%, a frequency of 1 Hz and a heating rate of 2 ° C. / min. Tan δ makes it possible to characterize the elasticity of the composition: the lower the tan δ, the greater the elastic recovery. The tan δ at 23° C. of the composition can be from 0.04 to 0.05, or from 0.05 to 0.06, or from 0.06 to 0.07, or from 0.07 to 0.08, or from 0.08 to 0.09, or from 0.09 to 0.10, or from 0.10 to 0.11, or from 0.11 to 0.12, or from 0.12 to 0.13, or from 0.13 to 0.14, or from 0.14 to 0.15, or from 0.15 to 0.16, or from 0.16 to 0.17, or from 0.17 to 0.18.

[0129] The composition according to the invention preferably has a density of less than or equal to 1.2, more preferentially less than or equal to 1.18. The density of the composition can be determined according to the ISO 1183-1 standard. In embodiments, the composition may have a density of 1.00 to 1.01, or 1.01 to 1.02, or 1.02 to 1.03, or 1.03 to 1.04, or 1.04 to 1.05, or 1.05 to 1.06, or 1.06 to 1.07, or 1.07 to 1.08, or 1.08 to 1.09, or 1.09 to 1.10, or 1.10 to 1.11, or 1.11 to 1.12, or 1.12 to 1.13, or 1.13 to 1.14, or 1.14 to 1.15, or 1.15 to 1.16, or 1.16 to 1.17, or 1.17 to 1.18, or 1.18 to 1.19, or 1.19 to 1.2.

[0130] The composition preferably has a Shore A hardness of 70 to 98, more preferably 75 to 95. The hardness measurement is performed according to the ISO 7619-1 standard.

[0131] The composition is advantageously in the form of granules. Alternatively, it may be in the form of a powder.

[0132] Advantageously, the TPU and PA compositions according to the invention comprise at least a portion of polyamide covalently bonded to at least a portion of thermoplastic polyether by means of urea functional groups. Preferably, the compositions according to the invention have a concentration of urea functional groups between 0.001 meq / g and 0.1 meq / g, preferably between 0.003 meq / g and 0.08 meq / g, more preferably between 0.005 meq / g and 0.05 meq / g. The concentration of urea functional groups can be determined by NMR according to the conditions described in the following article: "Reactivity of isocyanates with urethanes: Conditions for allophanate formation", Lapprand et al., Polymer Degradation and Stability, Vol. 90, No. 2, 2005, pp. 363-373.

[0133] Preferably, the portion of polyamide which is covalently bonded to at least a portion of the thermoplastic polyurethane by urea functional groups represents less than or equal to 10% by weight of the amount of polyamide, more preferably less than or equal to 5% by weight, more preferably less than or equal to 3% by weight and even more preferentially less than or equal to 2% by weight.

[0134] According to another aspect, the present invention relates to a composition obtained by reaction of at least one polyamide containing amine chain ends and at least one thermoplastic polyurethane or thermoplastic polyurethane precursor. The above characteristics can be applied in a similar manner to this aspect of the invention. In particular, the amounts of at least one polyamide containing amine chain ends and at least one thermoplastic polyurethane composition described above can therefore be applied to the amount of at least one polyamide containing amine chain ends and at least one thermoplastic polyurethane or thermoplastic polyurethane precursor reacted, respectively. The composition advantageously has a tensile modulus of less than or equal to 1000 MPa at 23°C.

[0135] Preparation method The present invention also relates to a method for preparing the above composition.

[0136] According to a first advantageous variant, the composition according to the invention can be prepared by a process comprising a step of mixing at least one polyamide comprising amine chain ends in the melt and at least one thermoplastic polyurethane in the melt, and optionally at least one copolymer containing polyamide blocks and polyether blocks in the melt, such a preparation process allows, under certain mixing time and temperature conditions, a reaction to take place between some of the amine functional groups of the polyamide and the urethane functional groups of the TPU, which improves the compatibility between the polyamide and the thermoplastic polyurethane.

[0137] Advantageously, the amount of polyamide containing amine chain ends in the molten state that is mixed is between 1% and 40% by weight, preferably between 1% and 30% by weight, the amount of thermoplastic polyurethane in the molten state that is mixed is between 10% and 99% by weight, preferably between 15% and 89% by weight, and the amount of copolymer containing polyamide blocks and polyether blocks is between 0 and 89% by weight, preferably between 10% and 70% by weight, relative to the total weight of the composition.

[0138] The mixing step can be carried out in any device known to the skilled artisan for mixing, kneading or extruding plastics in the molten state, such as an internal mixer, an open mill, an extruder, for example a single-screw extruder or a counter-rotating or co-rotating twin-screw extruder, a co-kneader, for example a continuous co-kneader, or a stirred reactor. Preferably, the mixing step is carried out in an extruder or co-kneader, more preferentially in an extruder, even more preferentially in a twin-screw extruder.

[0139] Preferably, the mixing step is carried out at a temperature greater than or equal to 160° C., preferably between 160° C. and 300° C., more preferably between 180° C. and 260° C. These temperature ranges allow optimal reaction between the polyamide containing amine chain ends and the thermoplastic polyurethane, and therefore better compatibility of the two polymers.

[0140] Advantageously, the mixing step is carried out for a period of between 30 seconds and 15 minutes, preferably between 40 seconds and 10 minutes. Preferably, the mixing step is carried out with stirring. These mixing conditions allow an optimal reaction between the polyamide containing amine chain ends and the thermoplastic polyurethane, and therefore a better compatibility of the two polymers.

[0141] The polyamide containing amine chain ends, the thermoplastic polyurethane, and optionally the copolymer containing polyamide blocks and polyether blocks, independently, can be in the form of a powder or granules prior to being melt-blended.

[0142] The mixing step can include mixing the polyamide containing amine chain ends, the thermoplastic polyurethane and optionally the copolymer containing polyamide blocks, and polyether blocks, in a molten state with other components of the composition (e.g., additives).

[0143] Advantageously, the preparation process includes a step of compacting the mixture in the form of granules or powder.

[0144] If the mixture is formed into a powder, it is preferably first formed into granules and then the granules are ground into a powder. Any type of mill can be used, such as a hammer mill, pin mill, attrition disc mill or impact classifier mill.

[0145] Preferably, the mixture is formed into granules.

[0146] According to another advantageous variant, the composition can be prepared by introducing, during the synthesis of at least one thermoplastic polyurethane, at least one polyamide comprising amine chain ends and optionally at least one copolymer containing polyamide blocks and polyether blocks. In such a preparation method, the polyamide comprising amine chain ends and optionally the copolymer containing polyamide blocks and polyether blocks are used as isocyanate-reactive compounds (as described above in the section "Thermoplastic polyurethanes (TPUs)"), optionally in addition to another isocyanate-reactive compound, preferably a polyol as described above, and / or a chain extender as described above.

[0147] Thus, the preparation method is - introducing the precursors of the thermoplastic polyurethane (i.e. at least one polyisocyanate, optionally at least one isocyanate-reactive compound, and optionally at least one chain extender) into a reactor; - introducing a polyamide containing amine chain ends into a reactor; - optionally introducing a copolymer containing polyamide blocks and polyether blocks into the reactor; - synthesizing a thermoplastic polyurethane in a reactor in the presence of a polyamide (and optionally a copolymer containing polyamide blocks and polyether blocks) comprising amine chain ends, resulting in a composition of thermoplastic polyurethane and polyamide (and optionally a copolymer containing polyamide blocks and polyether blocks).

[0148] Such a preparation method allows the reaction of some of the amine functional groups of the NH2 polyamide with some of the isocyanate functional groups of the polyisocyanate during the synthesis of the thermoplastic polyurethane, resulting in the formation of covalent bonds between the polyamide and the thermoplastic polyurethane, thereby improving the compatibility between the polyamide and the thermoplastic polyurethane.

[0149] Advantageously, relative to the total weight of the composition, the amount of polyamide containing amine chain ends introduced into the reactor is between 1% and 40% by weight, preferably between 1% and 30% by weight, the amount of thermoplastic polyurethane introduced into the reactor is between 10% and 99% by weight, preferably between 15% and 89% by weight, and the amount of copolymer containing polyamide blocks and polyether blocks introduced into the reactor is between 0 and 89% by weight, preferably between 10% and 70% by weight.

[0150] The steps of introducing the precursor of the thermoplastic polyurethane, introducing the polyamide containing amine chain ends, and introducing the copolymer containing polyamide blocks and polyether blocks can be simultaneous or can be carried out in any order. A catalyst can also be introduced into the reactor, as detailed above.

[0151] The reactor may be a batch reactor, a stirred reactor, a static mixer, an internal mixer, an open mill, an extruder, such as a single screw extruder, or a counter-rotating or co-rotating twin screw extruder, a continuous co-kneader, or a combination thereof. Preferably, the reactor is an extruder, more preferably a twin screw extruder.

[0152] Preferably, the step of synthesizing the thermoplastic polyurethane (in the presence of the polyamide containing amine chain ends and, optionally, the copolymer containing polyamide blocks and polyether blocks) is carried out at a temperature greater than or equal to 160° C., preferably between 160° C. and 300° C., more preferably between 180° C. and 270° C. These temperature ranges allow an optimal reaction between the polyamide containing amine chain ends and the thermoplastic polyurethane, and therefore a better compatibility of the two polymers.

[0153] The method may include introducing one or more additives into a reactor and mixing them in the reactor with the thermoplastic polyurethane, the polyamide including amine chain ends, and optionally the copolymer containing polyamide blocks and polyether blocks.

[0154] Preferably, the preparation process includes a step of compacting the composition in the form of granules or powder, more preferentially in the form of granules. The composition can be formed into a powder in the manner described above with reference to the first variant of the preparation process.

[0155] In these preparation methods, all the above-mentioned properties relating to the polyamides containing amine chain ends, the thermoplastic polyurethanes and the copolymers containing polyamide blocks and polyether blocks (particularly their nature, their amounts, etc.) can be applied in an analogous manner.

[0156] Generally, during preparation of the composition, the tensile modulus of the composition at 23° C. is: - by increasing the number average molar mass of the flexible blocks of the TPU (and / or PEBA, if present); - by using a material with a lower tensile modulus as flexible blocks of the TPU (and / or of the PEBA if present) a material; - by reducing the weight ratio of rigid blocks to flexible blocks of TPU (and / or PEBA, if present); It can be reduced by inducing a reaction between at least some of the PA containing amine chain ends and at least some of the TPU.

[0157] The present invention also relates to a composition obtained or obtainable by the above-mentioned preparation process, to which the properties described above, in particular in the "TPU and PA Compositions" section, can be applied in an analogous manner.

[0158] Purpose The compositions according to the invention can be used for the manufacture of sports equipment, for example sports footwear soles, ski footwear, midsoles, insoles or functional sole components in the form of inserts in various parts of the sole (for example the heel or arch), or footwear upper components in the form of reinforcements or inserts in the structure of the footwear upper, or in the form of protections.

[0159] It may also be used in the production of balls, sports gloves (eg football gloves), golf ball components, racquets, protective gear (jackets, helmet linings, shells, etc.).

[0160] The composition according to the invention can also be used for the production of various parts: - optical industry: components of eyeglass frames, nose pads or nose pieces, protection for frames; this is because the compositions of the invention have a soft, silky feel, adhere well to polyamides, more particularly transparent polyamides, by overmolding, and are resistant to sebum; Automotive industry: interior decoration; this is because the compositions according to the invention have a soft feel, good tactile properties, adhere perfectly by overmolding, are resistant to sebum and are abrasion resistant; manufacturing industry: transmission or conveyor belts, silent gears, because the compositions of the invention are heat-resistant, wear-resistant and easy to process by overmolding; - Medical: patches, biofeedback patches, drug delivery systems, sensors, catheters; - Electronics: headset components, earphones, Bluetooth® jewellery and watches, display screens, connected watches, connected glasses, interactive gaming components and devices, GPS, connected footwear, vital activity monitors and sensors, interactive belts and bracelets, child or pet trackers, pocket scanners or palmtops, location sensors, trackers or vision devices; - Transport industry: railway tie pads; - Toy industry; - Jewelry industry: watch bands.

[0161] Articles or components comprised of the above compositions may be produced by injection molding. EXAMPLES

[0162] The following examples illustrate the invention without, however, limiting it.

[0163] The following polymers were used: - TPU: A TPU with a rigid block based on 4,4'-MDI and 1,6-HDO (1,6-hexanediol) and a polyester flexible block based on adipic acid and butanediol, with a Shore A hardness of 95. PA no. 1: Polyamide 11 containing an average of one amine chain end per molecule and having a concentration of NH2 functional groups of 0.476 meq / g. PA no. 2: Polyamide 6 / 6.6 / 12 (40 / 25 / 35 by weight) containing amine chain ends and having a concentration of NH2 functional groups of 0.305 meq / g. PEBA no. 1: PEBA copolymer comprising rigid blocks of PA11 having a number average molar mass of 1000 g / mol and blocks of PTMG having a number average molar mass of 1000 g / mol. PEBA no. 2: PEBA copolymer comprising rigid blocks of PA11 with a number average molar mass of 4000 g / mol and flexible blocks of PTMG with a number average molar mass of 1000 g / mol.

[0164] Various compositions were prepared, the amounts of their components being indicated as percentages by weight in the table below. Table 1 TIFF2024517425000004.tif47170Table 2 TIFF2024517425000005.tif47170

[0165] All the above compositions were produced using an 18 mm ZSK twin screw extruder (Coperion). The barrel temperature was set at 210° C. and the screw speed was 280 rpm with a throughput of 8 kg / h.

[0166] The composition was then dried under reduced pressure at 80° C. to achieve a moisture content of less than 0.04%.

[0167] 1A test specimens (according to ISO 527) and 2 mm sheets were produced by injection moulding using a Battenfeld BA800 CDC press using an unpolished mould. The following parameters were applied during injection: - Barrel temperature: 180℃ - Nozzle temperature: 200℃ - Molding temperature: 30℃. - Cycle time: 60 seconds.

[0168] Compositions No. 1 to No. 8 are compositions according to the present invention, and compositions No. 9, No. 10 and No. 11 are comparative compositions.

[0169] Various properties of these compositions were evaluated: - Tensile modulus at 23°C: measured according to standard ISO 527-1A; - Stress at 50% strain at 23°C: measured according to standard ISO527-1A; - Elongation at break at 23°C: measured according to standard ISO 527-1A; - Breaking stress at 23°C: measured according to standard ISO 527-1A; - Density at 23°C: measured according to standard ISO1183-1; - Shore A hardness at 23°C: measured after 3s according to standard ISO7619-1; - tan δ at 23 °C: Measured according to standard ISO 6721 from 2019 at a tensile strain of 0.1%, a frequency of 1 Hz and a heating rate of 2 °C / min.

[0170] All of these evaluations were performed on dry (unconditioned) test specimens.

[0171] The results are presented in the table below. Table 3 TIFF2024517425000006.tif85170Table 4 TIFF2024517425000007.tif85170

[0172] Composition No. 1 is found to have a tan δ much lower than that of composition No. 9. Similarly, compositions No. 2, No. 3 and No. 4 have a lower loss factor (tan δ) than that of composition No. 10, and composition No. 8 has a lower loss factor (tan δ) than that of composition No. 11. The addition of a polyamide with NH2 chain ends therefore makes it possible to increase the elasticity of the composition.

[0173] Furthermore, the presence in the composition of a copolymer containing polyamide blocks and polyether blocks, in addition to the polyamide with NH2 chain ends, makes it possible to achieve lower densities.

[0174] It is also observed that compositions containing PA No. 1, which has a concentration of NH2 functional groups greater than that of PA No. 2, have a lower tan δ (and thus are more elastic) than compositions containing PA No. 2.

Claims

1. at least one thermoplastic polyurethane, and - comprises at least one polyamide containing an amine chain end, A composition, wherein the polyamide is a reaction product of one or more monomers selected from amino acids or aminocarboxylic acids, lactams, and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid.

2. at least one thermoplastic polyurethane or thermoplastic polyurethane precursor, and - obtained by reaction of at least one polyamide containing an amine chain end, A composition, wherein the polyamide is a reaction product of one or more monomers selected from amino acids or aminocarboxylic acids, lactams, and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid.

3. 3. The composition according to claim 1 or 2, wherein at least a portion of the polyamide is covalently bonded to at least a portion of the thermoplastic polyurethane by urea functional groups, the concentration of urea functional groups in the composition being preferably from 0.001 meq / g to 0.1 meq / g, more preferably from 0.003 meq / g to 0.08 meq / g, more preferably from 0.005 meq / g to 0.05 meq / g.

4. The polyamide has an NH ２ 3. The composition of claim 1 or 2 having a concentration of amine functional groups.

5. 3. The composition according to claim 1 or 2, having a tensile modulus at 23°C of 1000 MPa or less, preferably 800 MPa or less.

6. 3. The composition according to claim 1 or 2, further comprising at least one copolymer containing polyamide blocks and polyether blocks, preferably the polyamide blocks of the copolymer are selected from polyamide 6, polyamide 6.10, polyamide 6.12, polyamide 11, polyamide 10 and / or polyamide 12 blocks and / or the polyether blocks of the copolymer are polyethylene glycol and / or polytetrahydrofuran blocks.

7. 3. The composition according to claim 1 or 2, wherein the at least one polyamide comprising an amine chain end is present in an amount of up to 40% by weight, preferably up to 30% by weight, relative to the total weight of the composition.

8. By total weight of the composition: from 10% to 99% by weight, preferably from 15% to 89% by weight, of at least one thermoplastic polyurethane, - from 1% to 40% by weight, preferably from 1% to 30% by weight, of at least one polyamide with amine chain ends, and A composition according to claim 1 or 2, comprising from 0 to 89% by weight, preferably from 10% to 70% by weight, of at least one copolymer containing polyamide blocks and polyether blocks.

9. 3. A composition according to claim 1 or 2, having a tan δ at 23°C of 0.18 or less, preferably 0.16 or less.

10. 3. The composition according to claim 1, wherein the polyamide comprising amine chain ends has a number average molar mass of from 1000 to 60 000 g / mol, preferably from 2000 to 40 000 g / mol.

11. The thermoplastic polyurethane is a copolymer containing rigid and flexible blocks; the flexible blocks are selected from polyether blocks, polyester blocks, polycarbonate blocks and combinations thereof; preferably, the flexible blocks are selected from polyether blocks, polyester blocks and combinations thereof, and more preferentially are polytetrahydrofuran blocks, polypropylene glycol blocks and / or polyethylene glycol blocks; and / or A composition according to claim 1 or 2, in which the rigid block comprises units derived from diphenylmethane-4,4'-diisocyanate and / or hexamethylene-1,6-diisocyanate and preferably from at least one chain extender chosen from 1,3-propanediol, 1,4-butanediol and / or 1,6-hexanediol.

12. 3. The composition of claim 1 or 2, wherein the polyamide comprising amine chain ends is selected from the group consisting of polyamide 11, polyamide 12, polyamide 10, polyamide 6, polyamide 6.10, polyamide 6.6, polyamide 10.10, polyamide 10.12, and combinations thereof.

13. 3. The composition according to claim 1 or 2, wherein the polyamide has a concentration of COOH functional groups of from 0.002 meq / g to 0.2 meq / g, preferably from 0.005 meq / g to 0.1 meq / g, more preferably from 0.01 meq / g to 0.08 meq / g.

14. A method for preparing a composition comprising the steps of: mixing, preferably in an extruder, at least one polyamide comprising amine chain ends in the melt, at least one thermoplastic polyurethane in the melt and, optionally, at least one copolymer comprising polyamide blocks and polyether blocks in the melt, wherein the polyamide comprising amine chain ends is the reaction product of one or more monomers chosen from amino acids or aminocarboxylic acids, lactams and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid; - Optionally, shaping the mixture in the form of granules or powder. A method comprising:

15. A method for preparing a composition comprising the steps of: - introducing into a reactor, preferably an extruder, at least one precursor of a thermoplastic polyurethane; introducing into a reactor at least one polyamide comprising amine chain ends and optionally at least one copolymer comprising polyamide blocks and polyether blocks, the polyamide comprising amine chain ends being the reaction product of one or more monomers selected from amino acids or aminocarboxylic acids, lactams, and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid; - synthesizing a thermoplastic polyurethane in a reactor in the presence of a polyamide containing amine chain ends to obtain a composition made of thermoplastic polyurethane and polyamide; - Optionally, the process comprises the step of compacting the composition in the form of granules or powder.

16. 3. An article consisting of or comprising at least one element consisting of a composition according to claim 1 or 2, preferably selected from footwear soles for sports, large or small balls, gloves, personal protective equipment, tie pads, automotive parts, structural parts, optical equipment parts, electrical and electronic equipment parts, watch bands, toys, medical equipment parts such as catheters, transmission or conveyor belts, gears and production line conveyor belts.

17. The following steps: - providing a composition according to claim 1 or 2; - injection molding said composition A method of manufacturing an article, comprising:

3. A method according to claim 1, wherein the article is an article consisting of or comprising at least one element consisting of the composition according to claim 1 or 2, preferably selected from footwear soles for sports, large or small balls, gloves, personal protective equipment, tie pads, automotive parts, structural parts, optical equipment parts, electrical and electronic equipment parts, watch bands, toys, medical equipment parts such as catheters, transmission or conveyor belts, gears and production line conveyor belts.