Compositions containing thermoplastic polyurethanes and copolymers having polyamide blocks and polyether blocks containing amine chain ends - Patents.com

Abstract

The present invention relates to compositions comprising at least one thermoplastic polyurethane and at least one copolymer containing polyamide blocks and polyether blocks comprising amine chain ends, the composition having a tensile modulus of 170 MPa or less at 23° C. The present invention also relates to compositions obtained by reaction of at least one copolymer containing polyamide blocks and polyether blocks comprising amine chain ends and at least one thermoplastic polyurethane, or a thermoplastic polyurethane precursor, methods for preparing such compositions, and articles made therefrom.

Description

[Technical field]

[0001] The present invention relates to compositions based on thermoplastic polyurethanes and copolymers containing polyamide and polyether blocks and to a process for their preparation. [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 compression or tensile permanent set, 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 polyurethane resin compositions comprising thermoplastic polyurethane resins prepared by dry blending of components, and copolymers containing polyamide blocks and polyether blocks, the copolymers containing polyamide blocks and the polyether blocks being formed by polymerizing triblock polyetherdiamines, dicarboxylic acids and polyamide-forming monomers. These compositions have an extremely high tensile modulus of more than 1110 MPa.

[0007] There is a practical need to provide compositions that have good tear strength, high elasticity, low density, good flexibility and low tensile set. Summary of the Invention

[0008] The present invention first provides a composition comprising: at least one thermoplastic polyurethane, - at least one copolymer containing polyamide blocks and polyether blocks containing amine chain ends, The composition has a tensile modulus of 170 MPa or less at 23°C.

[0009] The present invention relates to: - at least one copolymer containing polyamide blocks and polyether blocks comprising amine chain ends, and a composition obtained by reaction of at least one thermoplastic polyurethane or thermoplastic polyurethane precursor, It also relates to compositions having a tensile modulus at 23°C of 170 MPa or less.

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

[0011] In an embodiment, the copolymer containing polyamide blocks and polyether blocks has a concentration of NH2 amine functional groups from 0.01 meq / g to 1 meq / g, preferably from 0.02 meq / g to 0.4 meq / g.

[0012] In an embodiment, the composition has a tan δ at 23° C. less than or equal to 0.12.

[0013] In an embodiment, the composition comprises, based on the total weight of the composition: - 15% to 70% by weight, preferably 20% to 60% by weight, of at least one thermoplastic polyurethane, and - comprises from 30% to 85% by weight, preferably from 40% to 80% by weight, of at least one copolymer containing polyamide blocks and polyether blocks containing amine chain ends.

[0014] In an embodiment, the composition has a density less than or equal to 1.16, preferably less than or equal to 1.14.

[0015] In an embodiment, the composition has a tensile set of 15% or less, preferably 13% or less, after 10 cycles at 30% strain.

[0016] In an embodiment, the molar ratio of urethane functional groups to NH2 amine functional groups of the assembly consisting of at least one copolymer containing polyamide blocks and polyether blocks with amine chain ends and at least one thermoplastic polyurethane is between 15 and 350, preferably between 25 and 250 and more preferentially between 40 and 200.

[0017] 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;

[0018] In an embodiment, the polyamide blocks of the copolymers containing polyamide blocks and polyether blocks comprising amine chain ends are polyamide 11, polyamide 12, polyamide 10, polyamide 6, polyamide 6.10, polyamide 6.12, polyamide 10.10 and / or polyamide 10.12 blocks, preferably polyamide 11, polyamide 12, polyamide 6 and / or polyamide 6.12 blocks; and / or the polyether blocks of the copolymers containing polyamide blocks and polyether blocks comprising amine chain ends are polyethylene glycol blocks and / or polytetrahydrofuran blocks.

[0019] 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 copolymer containing polyamide blocks and polyether blocks comprising amine chain ends in the molten state with at least one thermoplastic polyurethane in the molten state; - optionally forming the mixture in the form of granules or powder; The composition also relates to a method, wherein the composition has a tensile modulus at 23° C. of 170 MPa or less.

[0020] 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 the reactor at least one copolymer containing polyamide blocks and polyether blocks comprising amine chain ends; - synthesizing a thermoplastic polyurethane in a reactor in the presence of a copolymer containing polyamide blocks and polyether blocks comprising amine chain ends to obtain a composition made of thermoplastic polyurethane and a copolymer containing polyamide blocks and polyether blocks; and - optionally forming the composition in the form of granules or powder, The composition also relates to a method, wherein the composition has a tensile modulus at 23° C. of 170 MPa or less.

[0021] 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.

[0022] 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.

[0023] The present invention makes it possible to meet the demands mentioned above, more particularly by providing a low density composition which simultaneously exhibits high elasticity and high flexibility, low tensile set and high tear strength and durability.

[0024] This is accomplished through the combination of a thermoplastic polyurethane (or TPU) and a copolymer (or PEBA) containing polyamide and polyether blocks with amine (NH2) chain ends and a specific tensile modulus of composition.

[0025] In one advantageous embodiment, the reaction occurs between at least a portion of the copolymer containing polyamide blocks and polyether blocks with amine chain ends and at least a portion of the thermoplastic polyurethane, more particularly between the amine functional groups of the copolymer containing polyamide blocks and polyether blocks 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 copolymer containing polyamide blocks and polyether blocks with 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, in particular the properties mentioned above. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] The invention is explained in more detail below and in a non-limiting manner in the description that follows.

[0027] The present invention relates to a composition comprising at least one thermoplastic polyurethane and at least one copolymer containing a polyamide block and a polyether block having an amine chain end. In this context, the terms "chain end" and "chain end" have the same meaning and may be used interchangeably.

[0028] Copolymers containing polyamide blocks and polyether blocks (PEBA) The PEBA according to the present invention has amine chain ends.

[0029] The PEBAs according to the invention result from the polycondensation of polyamide blocks (rigid or hard blocks) carrying reactive ends and polyether blocks (flexible or soft blocks) carrying reactive ends, in particular of polyamide blocks carrying dicarboxyl chain ends and of polyoxyalkylene blocks carrying diamine chain ends, obtainable, for example, by cyanoethylation and hydrogenation of α,ω-dihydroxylated aliphatic polyoxyalkylene blocks known as polyether diols.

[0030] Polyamide blocks carrying dicarboxyl chain ends result, for example, from the condensation of polyamide precursors in the presence of dicarboxylic acid chain limiters.

[0031] Three types of polyamide blocks can be advantageously used.

[0032] According to a first type, the polyamide blocks result from the condensation of dicarboxylic acids, in particular those having from 4 to 36 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 20 carbon atoms and preferably those having from 6 to 14 carbon atoms.

[0033] 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.

[0034] Examples of diamines may 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), para-aminodicyclohexylmethane (PACM), isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN) and piperazine (Pip).

[0035] Advantageously, the polyamide blocks PA4.12, PA4.14, PA4.18, 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 originating from the diamine residue and Y represents the number of carbon atoms originating from the diacid residue.

[0036] 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 having 6 to 12 carbon atoms in the presence of a dicarboxylic acid having 4 to 18 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.

[0037] Advantageously, the second type of polyamide block is a block of 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.

[0038] 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.

[0039] In this case, the polyamide block PA - 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.

[0040] 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).

[0041] According to a variant of this third type, the polyamide blocks result 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 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.

[0042] Examples of polyamide blocks of the third type 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.

[0043] The notations PAX / Y, PAX / Y / Z etc. refer to copolyamides where X, Y, Z etc. represent homopolyamide units as defined above.

[0044] Advantageously, the polyamide blocks of the copolymers used according to the invention are selected from the group consisting of 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, PA10.16, PA10.18, PA10.36, A10.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 blocks of polyamides PA6, PA10, PA11, PA12, PA6.10, PA6.12, PA10.10, PA10.12, or mixtures or copolymers thereof, more preferentially blocks of polyamides PA11, PA12, PA6, PA6.12, or mixtures or copolymers thereof.

[0045] The polyether blocks consist of alkylene oxide units.

[0046] 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 blocks, i.e. blocks made up of tetramethylene glycol units, also known as polytetrahydrofuran. PEBA copolymers may contain several types of polyether in their chains, the copolyethers being optionally in block or random form.

[0047] 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.

[0048] The polyether blocks may also be comprised of ethoxylated primary amines. Examples of ethoxylated primary amines include those of the formula: TIFF2024517424000001.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®.

[0049] The polyether flexible block according to the invention comprises 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, ED 2003 or XTJ 542, commercial products from Huntsman and also described in documents JP2004346274, JP2004352794 and EP1482011).

[0050] The polyetherdiol blocks are thus aminated in order to convert them into polyetherdiamines and condense with the carboxyl-terminated polyamide blocks. The general methods for preparing PEBA copolymers bearing amide bonds between the PA and PE blocks are known and are described, for example, in the document EP1482011. The polyether blocks can also be mixed with polyamide precursors and diacid chain limiters to prepare polymers containing polyamide blocks and polyether blocks with randomly distributed units (one-step process). Polyetherdiols bearing OH chain ends can be present as aminated polyetherdiols when condensed with the polyamide blocks. These polyetherdiols bearing OH chain ends can be condensed with the carboxyl-terminated polyamide blocks, forming ester bonds between the PA and PE blocks (the resulting product is a polyetheresteramide).

[0051] 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.

[0052] While the above block-containing copolymers generally comprise at least one polyamide block and at least one polyether block, the present invention also covers copolymers comprising two, three, four (or even more) different blocks selected from those described herein, provided that these blocks comprise at least polyamide and polyether blocks.

[0053] For example, the copolymer according to the invention may be a segmented block copolymer (or "triblock" copolymer) comprising three different types of blocks, 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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:

[0058] 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.

[0059] 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.

[0060] 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.

[0061] Preferably, the copolymer used in the present invention has a Shore D hardness of 30 or more. Preferably, the copolymer used in the present invention has an instantaneous hardness of 65 Shore A to 80 Shore D, more preferably 75 Shore A to 65 Shore D, and more preferentially 80 Shore A to 55 Shore D. Hardness measurements can be carried out according to standard ISO 7619-1.

[0062] Advantageously, the PEBA according to the invention has a concentration of NH2 functional groups between 0.01 meq / g and 1 meq / g, preferably between 0.02 meq / g and 0.4 meq / g. The PEBA has a concentration of NH2 functional groups between 0.01 and 0.015 meq / g, or between 0.015 and 0.02 meq / g, or between 0.02 and 0.025 meq / g, or between 0.025 and 0.03 meq / g, or between 0.03 and 0.035 meq / g, or between 0.035 and 0.04 meq / g, or between 0.04 and 0.045 meq / g, or between 0.045 and 0.05 meq / g, or between 0.05 and 0.06 meq / g, or between 0.06 and 0.07 meq / g, or between 0.07 and 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.

[0063] The PEBA according to the present invention 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 PEBA according to the present 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.

[0064] The PEBA according to the invention may contain hydroxyl (OH) chain ends (e.g. resulting from the condensation of a polyether diol carrying OH chain ends with a carboxyl-terminated polyamide block). In particular, the PEBA according to the invention may have a concentration of OH functionality (i.e. of hydroxyl chain ends) of 0.002-0.2 meq / g, preferably 0.005-0.05 meq / g. The concentration of OH functionality 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.

[0065] Thermoplastic Polyurethane (TPU) The thermoplastic polyurethanes according to the present invention are copolymers of rigid and flexible blocks.

[0066] 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.

[0067] 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.

[0068] The polyisocyanates may be aliphatic, cycloaliphatic, araliphatic and / or aromatic. Preferably, the polyisocyanates are diisocyanates.

[0069] 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.

[0070] 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.

[0071] Even more preferably, the polyisocyanate is 4,4'-MDI (diphenylmethane-4,4'-diisocyanate), 1,6-HDI (hexamethylene-1,6-diisocyanate) or a mixture thereof.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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).

[0076] 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.

[0077] 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.

[0078] 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, and n, m and p each independently preferably represent an integer between 0 and 50, with m more preferably between 1 and 50, and even more preferentially between 2 and 50]. Preferably, the polysiloxane has the following formula (II): TIFF2024517424000002.tif18170 [wherein Me is a methyl group] or the following formula (III): I have TIFF2024517424000003.tif15170.

[0079] The polyalkylene diols which can be used in the present invention are preferably butadiene-based.

[0080] 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.

[0081] One or more polyols may be used as the isocyanate-reactive compound.

[0082] Particularly preferably, the flexible blocks of TPU are blocks of polytetrahydrofuran, polypropylene glycol and / or polyethylene glycol.

[0083] Preferably, a chain extender is used in addition to the isocyanate and the isocyanate-reactive compound in preparing the thermoplastic polyurethane.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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).

[0092] 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.

[0093] Advantageously, the TPU may be a recycled TPU and / or a partially or fully bio-based TPU.

[0094] 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.

[0095] 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.

[0096] TPU and PEBA Composition The composition according to the invention is a blend comprising at least one PEBA and at least one TPU. 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).

[0097] The composition according to the invention advantageously comprises, relative to the total weight of the composition, from 20% to 95% by weight of at least one copolymer containing polyamide blocks and polyether blocks with amine chain ends and from 5% to 80% by weight of at least one thermoplastic polyurethane, more preferentially from 30% to 85% by weight of at least one copolymer containing polyamide blocks and polyether blocks with amine chain ends and from 15% to 70% by weight of at least one thermoplastic polyurethane, even more preferentially from 40% to 80% by weight of at least one copolymer containing polyamide blocks and polyether blocks with amine chain ends and from 20% to 60% by weight of at least one thermoplastic polyurethane.In an embodiment, the composition comprises, relative to the total weight of the composition, 20% to 30% by weight of at least one copolymer containing a polyamide block and a polyether block with amine chain ends, and 70% to 80% by weight of at least one thermoplastic polyurethane, or 30% to 40% by weight of at least one copolymer containing a polyamide block and a polyether block with amine chain ends, and 60% to 70% by weight of at least one thermoplastic polyurethane, or 40% to 50% by weight of at least one copolymer containing a polyamide block and a polyether block with amine chain ends, and 50% to 60% by weight of at least one thermoplastic polyurethane, or 50% to 60% by weight of at least one copolymer containing a polyamide block and a polyether block with amine chain ends, and 40% to 50% by weight of at least one thermoplastic polyurethane. % of at least one copolymer containing polyamide blocks and polyether blocks with amine chain ends, and 30% to 40% by weight of at least one thermoplastic polyurethane, or 70% to 80% by weight of at least one copolymer containing polyamide blocks and polyether blocks with amine chain ends, and 20% to 30% by weight of at least one thermoplastic polyurethane, or 80% to 90% by weight of at least one copolymer containing polyamide blocks and polyether blocks with amine chain ends, and 10% to 20% by weight of at least one thermoplastic polyurethane, or 90% to 95% by weight of at least one copolymer containing polyamide blocks and polyether blocks with amine chain ends, and 5% to 10% by weight of at least one thermoplastic polyurethane.

[0098] The molar ratio of urethane functional groups to NH2 amine functional groups of the assembly of at least one copolymer containing polyamide blocks and polyether blocks with 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.

[0099] The composition according to the invention may consist of at least one copolymer containing polyamide blocks and polyether blocks comprising amine chain ends, and at least one thermoplastic polyurethane.

[0100] 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.

[0101] The composition according to the invention has a tensile modulus at 23°C of less than or equal to 170 MPa. The tensile modulus of the composition can be determined according to standard ISO 527-1A. More preferably, the tensile modulus of the composition at 23°C is less than or equal to 150 MPa. In particular, this may be between 20 and 30 MPa, or between 30 and 40 MPa, or between 40 and 50 MPa, or between 50 and 60 MPa, or between 60 and 70 MPa, or between 70 and 80 MPa, or between 80 and 90 MPa, or between 90 and 100 MPa, or between 100 and 110 MPa, or between 110 and 120 MPa, or between 120 and 130 MPa, or between 130 and 140 MPa, or between 140 and 150 MPa, or between 150 and 160 MPa, or between 160 and 170 MPa.

[0102] Preferably, the weight of the total flexible block (i.e. the flexible block of thermoplastic polyurethane and PEBA) is between 10% and 95%, more preferentially between 30% and 90%, and even more preferentially between 50% and 85% of the total weight of PEBA and TPU. The total flexible block may in particular be between 10% and 20%, or between 20% and 30%, or between 30% and 40%, or between 40% and 50%, or between 50% and 60%, or between 60% and 70%, or between 70% and 80%, or between 80% and 90%, or between 90% and 95% of the total weight of PEBA and TPU. The weight of the total flexible block can be determined by nuclear magnetic resonance (NMR).

[0103] Advantageously, the composition has a tan δ at 23 ° C less than or equal to 0.12, preferably less than or equal to 0.11, advantageously less than or equal to 0.10. 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 the 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 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 0.12.

[0104] The composition according to the invention preferably has a density of 1.16 or less, more preferentially 1.14 or less, advantageously 1.12 or less. The density of the composition can be determined according to the ISO 1183-1 standard. In an embodiment, 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.

[0105] The composition preferably has a Shore A hardness of 70 to 98, more preferably 75 to 95. Hardness measurements may be performed according to the ISO 7619-1 standard.

[0106] The composition may advantageously have a tensile set of 15% or less, preferably 13% or less, after 10 cycles at 30% strain. Tensile set may be determined as indicated below in the "Examples" section.

[0107] The composition is advantageously in the form of granules. Alternatively, it may be in the form of a powder.

[0108] Advantageously, the TPU and PEBA composition according to the invention comprises at least a portion of a thermoplastic polyether, at least a portion of a copolymer containing polyamide blocks and polyether blocks covalently bonded by urea functional groups.

[0109] Preferably, the composition according to the invention has a concentration of urea functional groups of 0.001 meq / g to 0.1 meq / g, preferably 0.003 meq / g to 0.08 meq / g, more preferably 0.005 meq / g to 0.05 meq / g. The concentration of urea functional groups can be determined by NMR according to the conditions described in the following paper: "Reactivity of isocyanates with urethanes: Conditions for allophanate formation", Lapprand et al., Polymer Degradation and Stability, Vol. 90, No. 2, 2005, pp. 363-373.

[0110] Preferably, the part of the copolymer containing polyamide blocks and polyether blocks which is covalently bonded by urea functional groups to at least a portion of the thermoplastic polyurethane represents not more than 10% by weight, more preferably not more than 5% by weight, more preferably not more than 3% by weight and even more preferentially not more than 2% by weight of the amount of the copolymer containing polyamide blocks and polyether blocks.

[0111] According to another aspect, the present invention relates to a composition obtained by reaction of at least one copolymer containing polyamide blocks and polyether blocks 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. Thus, in detail, the amounts of the composition of at least one copolymer containing polyamide blocks and polyether blocks containing amine chain ends and at least one thermoplastic polyurethane can be applied to the amount of at least one copolymer containing polyamide blocks and polyether blocks containing amine chain ends and at least one thermoplastic polyurethane or thermoplastic polyurethane precursor reacted, respectively. The composition has a tensile modulus of 170 MPa or less at 23°C.

[0112] Preparation method The present invention also relates to a method for preparing the above composition.

[0113] According to a first advantageous variant, the composition according to the invention can be prepared by a process comprising a step of mixing, in the molten state, at least one copolymer containing polyamide blocks and polyether blocks comprising amine chain ends with at least one thermoplastic polyurethane, 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 copolymer containing polyamide blocks and polyether blocks and the urethane functional groups of the TPU, which improves the compatibility between the copolymer containing polyamide blocks and polyether blocks and the thermoplastic polyurethane.

[0114] Advantageously, the amount of copolymer containing polyamide blocks and polyether blocks containing amine chain ends in the molten state that is mixed, relative to the total weight of the composition, is between 20% and 95% by weight, preferably between 30% and 85% by weight and more preferentially between 40% and 80% by weight, and the amount of thermoplastic polyurethane in the molten state that is mixed is between 5% and 80% by weight, preferably between 15% and 70% by weight and more preferentially between 20% and 60% by weight.

[0115] 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.

[0116] 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 copolymer containing polyamide blocks and polyether blocks with amine chain ends and the thermoplastic polyurethane, and therefore better compatibility of the two polymers.

[0117] 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 copolymer containing polyamide blocks and polyether blocks with amine chain ends and the thermoplastic polyurethane, and therefore a better compatibility of the two polymers.

[0118] The copolymer containing the polyamide blocks and polyether blocks containing amine chain ends and the thermoplastic polyurethane, independently, can be in powder or granular form prior to being melt-blended.

[0119] The step of mixing can include mixing the copolymer containing the polyamide blocks and polyether blocks containing amine chain ends and the thermoplastic polyurethane in a molten state with other components of the composition (e.g., additives).

[0120] Advantageously, the preparation process includes a step of compacting the mixture in the form of granules or powder.

[0121] 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.

[0122] Preferably, the mixture is formed into granules.

[0123] According to another advantageous variant, the composition can be prepared by introducing at least one copolymer containing a polyamide block and a polyether block containing amine chain ends during the synthesis of at least one thermoplastic polyurethane. In such a preparation method, the copolymer containing a polyamide block and a polyether block containing amine chain ends is used as an isocyanate-reactive compound (as described above in the "Thermoplastic Polyurethanes (TPUs)" section), optionally in addition to another isocyanate-reactive compound, preferably a polyol as described above, and / or a chain extender as described above.

[0124] 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 into the reactor a copolymer containing polyamide blocks and polyether blocks comprising amine chain ends; - synthesizing a thermoplastic polyurethane in a reactor in the presence of a copolymer containing polyamide blocks and polyether blocks comprising amine chain ends, resulting in a composition of thermoplastic polyurethane and copolymer containing polyamide blocks and polyether blocks.

[0125] Such a preparation method allows the reaction of some of the NH2 amine functional groups of the copolymer containing polyamide blocks and polyether blocks 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 copolymer containing polyamide blocks and polyether blocks and the thermoplastic polyurethane, thereby improving the compatibility between the copolymer containing polyamide blocks and polyether blocks and the thermoplastic polyurethane.

[0126] Advantageously, the amount of copolymer containing polyamide blocks and polyether blocks comprising amine chain ends introduced into the reactor is between 20% and 95% by weight, preferably between 30% and 85% by weight and more preferentially between 40% and 80% by weight, relative to the total weight of the composition, and the amount of thermoplastic polyurethane precursor introduced into the reactor is between 5% and 80% by weight, preferably between 15% and 70% by weight and more preferentially between 20% and 60% by weight.

[0127] The steps of introducing the precursor of the thermoplastic polyurethane and the copolymer containing the polyamide block and the polyether block with amine chain ends can be simultaneous or can be carried out in any order. A catalyst can also be introduced into the reactor, as described in detail above.

[0128] 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.

[0129] Preferably, the step of synthesizing the thermoplastic polyurethane (in the presence of the copolymer containing polyamide blocks and polyether blocks with amine chain ends) 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 copolymer containing polyamide blocks and polyether blocks with amine chain ends and the thermoplastic polyurethane, and therefore a better compatibility of the two polymers.

[0130] The method can include introducing one or more additives into a reactor and mixing them in the reactor with the thermoplastic polyurethane and the copolymer containing polyamide blocks and polyether blocks with amine chain ends.

[0131] 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.

[0132] In these preparation methods, all the above-mentioned properties relating to the copolymers containing polyamide blocks and polyether blocks and to the thermoplastic polyurethanes (particularly their nature, their amounts, etc.) can be applied in an analogous manner.

[0133] 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 PEBA and / or TPU; - By using materials with lower tensile modulus as flexible blocks of PEBA and / or TPU; - by reducing the weight ratio of rigid blocks to flexible blocks (PEBA and / or TPU); It can be reduced by inducing a reaction between at least a portion of the PEBA containing amine chain ends and at least a portion of the TPU.

[0134] 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 PEBA composition" section, can be applied in an analogous manner.

[0135] 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.

[0136] 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.).

[0137] 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.

[0138] Articles or components comprised of the above compositions may be produced by injection molding. EXAMPLES

[0139] The following examples illustrate the invention without, however, limiting it.

[0140] The following polymers were used: - TPU No. 1: 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. - TPU No. 2: TPU with a rigid block based on 4,4'-MDI and 1,6-HDO (1,6-hexanediol) and with a polyester flexible block based on adipic acid and butanediol, with a Shore D hardness of 59. - PEBA: PEBA copolymer with amine chain ends (copolymer of PTMG and PPG) comprising a rigid block of polyamide 11 with amine chain ends and a flexible block of polyether, the rigid block of polyamide 11 having a number average molar mass of 1000 g / mol and the flexible block of polyether having a number average molar mass of 1000 g / mol, the PEBA copolymer having a concentration of NH2 functional groups of 0.032 meq / g.

[0141] Various compositions were prepared, the amounts of their components being indicated as percentages by weight in the table below. TIFF2024517424000004.tif34170

[0142] 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.

[0143] The composition was then dried under reduced pressure at 80° C. to achieve a moisture content of less than 0.04%.

[0144] 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.

[0145] Compositions No. 1 and No. 2 are compositions according to the invention, and composition No. 3 is a comparative composition.

[0146] 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: measured according to standard ISO 527-1A; - Breaking stress: measured according to standard ISO527-1A; - Tensile set and hysteresis area: Hysteresis tests carried out to determine the permanent set and hysteresis area after 10 cycles at 30% strain were carried out under the conditions detailed below: ○ Sample: Type 1A test specimen according to standard ISO 527; Conditioning: 2 weeks at 23°C and 50% relative humidity; ○Dynamometer: Zwick 1; ○L0: 75mm; Test speed: 200mm / min; Distortion: 30%; Number of cycles: 10. - 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.

[0147] All of these evaluations were performed on dry (unconditioned) test specimens.

[0148] The results are presented in the table below. TIFF2024517424000005.tif67170

[0149] The compositions according to the invention have a lower tensile set than the comparative compositions; articles made from such compositions are found to be more durable than articles made from the comparative compositions.

[0150] Furthermore, the compositions according to the invention have a lower loss factor (tan δ) at 23° C. than that of the comparative composition and therefore have higher elasticity than the comparative composition whilst retaining a low density.

Claims

1. 1. A composition comprising: at least one thermoplastic polyurethane, - comprises at least one copolymer containing polyamide blocks and polyether blocks containing amine chain ends, The composition has a tensile modulus of 170 MPa or less at 23°C.

2. at least one copolymer containing polyamide blocks and polyether blocks containing amine chain ends, and at least one thermoplastic polyurethane or thermoplastic polyurethane precursor A composition obtained by the reaction of The composition has a tensile modulus of 170 MPa or less at 23°C.

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

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

5. 3. The composition of claim 1 or 2 having a tan δ of 0.12 or less at 23°C.

6. By total weight of the composition: - from 15% to 70% by weight, preferably from 20% to 60% by weight, of at least one thermoplastic polyurethane, and A composition according to claim 1 or 2, comprising from 30% to 85% by weight, preferably from 40% to 80% by weight, of at least one copolymer containing polyamide blocks and polyether blocks comprising amine chain ends.

7. 3. The composition according to claim 1 or 2, having a density of less than or equal to 1.16, preferably less than or equal to 1.

14.

8. 3. The composition of claim 1 or 2, having a tensile set of 15% or less, preferably 13% or less, after 10 cycles at 30% strain.

9. For an assembly consisting of at least one copolymer containing polyamide blocks and polyether blocks with amine chain ends, and at least one thermoplastic polyurethane, the urethane functional groups are ２ 3. Composition according to claim 1 or 2, in which the molar ratio to the amine functions is between 15 and 350, preferably between 25 and 250, and more preferentially between 40 and 200.

10. 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.

11. 3. The composition according to claim 1, wherein the polyamide blocks of the copolymers containing polyamide blocks and polyether blocks comprising amine chain ends are polyamide 11, polyamide 12, polyamide 10, polyamide 6, polyamide 6.10, polyamide 6.12, polyamide 10.10 and / or polyamide 10.12 blocks, preferably polyamide 11, polyamide 12, polyamide 6 and / or polyamide 6.12 blocks; and / or the polyether blocks of the copolymers containing polyamide blocks and polyether blocks comprising amine chain ends are polyethylene glycol blocks and / or polytetrahydrofuran blocks.

12. A method for preparing a composition comprising the steps of: mixing, preferably in an extruder, at least one copolymer containing polyamide blocks and polyether blocks comprising amine chain ends in the molten state with at least one thermoplastic polyurethane in the molten state; - Optionally, shaping the mixture in the form of granules or powder. Including; The method, wherein the composition has a tensile modulus at 23° C. of 170 MPa or less.

13. 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 the reactor at least one copolymer containing polyamide blocks and polyether blocks comprising amine chain ends; - synthesizing in a reactor a thermoplastic polyurethane in the presence of a copolymer containing polyamide blocks and polyether blocks comprising amine chain ends, resulting in a composition made of a thermoplastic polyurethane and a copolymer containing polyamide blocks and polyether blocks; - optionally shaping the composition in the form of granules or powder; Including; The method, wherein the composition has a tensile modulus at 23° C. of 170 MPa or less.

14. 3. An article consisting of or comprising at least one element consisting of a composition according to claim 1 or 2, 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.

15. 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 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.