Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/02—Polyureas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/06—Polyurethanes from polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
  • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
  • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
  • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
  • B29K2075/02—Polyureas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2120/00—Compositions for reaction injection moulding processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/04—Thermoplastic elastomer

Definitions

• the present invention relates to compositions based on thermoplastic polyurethane and copolymer with polyamide blocks and with polyether blocks, as well as processes for their preparation.
• polymer compositions are used in particular in the field of sports equipment, such as soles or sole components, gloves, rackets or golf balls, or individual protection elements in particular for the practice of sport (vests, interior parts of helmets, shells, etc.). Such applications require a set of particular physical properties ensuring an ability to rebound, a low residual deformation after compression or traction and an ability to endure repeated impacts and to return to the initial shape.
• the polymer compositions are also used, for example, in the field of medical equipment, such as catheters, or in other fields (for example for watch straps, toys or industrial applications, in particular for conveyor belts for production lines).
• Document FR 2831175 relates to a composition
• a composition comprising a mixture of at least two thermoplastic polyurethanes and a compatibilizer in an amount less than or equal to 15%, the compatibilizer preferably being a polyetheramide, a polyesteramide or a polyetheresteramide.
• JP 5393036 describes a thermoplastic resin composition comprising a thermoplastic resin and an antistatic agent containing a polyetheresteramide and a polyurethane-based thermoplastic elastomer.
• Patent JP 5741139 describes polyurethane resin compositions comprising a thermoplastic polyurethane resin and a copolymer with polyamide blocks and polyether blocks, prepared by dry mixing the components, in which the copolymer with polyamide blocks and polyether blocks is formed by the polymerization of a polyether diamine triblock, a dicarboxylic acid and a polyamide-generating monomer. These compositions have a very high tensile modulus, greater than 1110 MPa.
• the invention relates firstly to a composition
• a composition comprising:
• thermoplastic polyurethane - at least one thermoplastic polyurethane
• composition having a tensile modulus at 23° C. of less than or equal to 170 MPa.
• the invention also relates to a composition obtained by the reaction of:
• thermoplastic polyurethane or thermoplastic polyurethane precursors said composition having a tensile modulus at 23° C. of less than or equal to 170 MPa.
• At least a part of the polyamide block and polyether block copolymer is covalently bonded to at least a part of the thermoplastic polyurethane by a urea function, the concentration of urea function of the composition preferably being 0.001 to 0.1 meq/g, more preferably from 0.003 to 0.08 meq/g, even more preferably from 0.005 to 0.05 meq/g.
• the copolymer with polyamide blocks and with polyether blocks has an amine function concentration Nhte of 0.01 meq/g to 1 meq/g, preferably of 0.02 meq/g to 0.4 meq/ g.
• the composition has a tan d at 23°C of less than or equal to 0.12. In embodiments, the composition comprises, based on the total weight of the composition:
• thermoplastic polyurethane from 15 to 70% by weight, preferably from 20 to 60% by weight, of at least one thermoplastic polyurethane
• the composition has a density less than or equal to 1.16, preferably less than or equal to 1.14.
• the composition has a tensile set after 10 cycles of 30% deformation of less than or equal to 15%, preferably less than or equal to 13%.
• the molar ratio of the urethane functions to the amine functions Nhte of the assembly consisting of at least one copolymer with polyamide blocks and with polyether blocks comprising ends of the amine chain and of the at least one thermoplastic polyurethane is 15 to 350, preferably from 25 to 250, more preferably from 40 to 200.
• the thermoplastic polyurethane is a copolymer with rigid blocks and with flexible blocks, in which:
• the flexible blocks are chosen from polyether blocks, polyester blocks, polycarbonate blocks and a combination thereof, preferably the flexible blocks are chosen from polyether blocks, polyester blocks, and a combination thereof, and are more preferably blocks of polytetrahydrofuran, polypropylene glycol and/or polyethylene glycol; and or
• the rigid blocks comprise units derived from 4,4'-diphenylmethane diisocyanate and/or 1,6-hexamethylene diisocyanate and, preferably, units derived from at least one chain extender chosen from 1,3-propanediol , 1,4-butanediol, and/or 1,6-hexanediol.
• the polyamide blocks of the copolymer with polyamide blocks and with polyether blocks comprising amine chain ends are blocks of polyamide 11, of polyamide 12, of polyamide 10, of polyamide 6, of polyamide 6.10, of polyamide 6.12 , of polyamide 10.10 and/or of polyamide 10.12, preferably of polyamide 11, of polyamide 12, of polyamide 6 and/or of polyamide 6.12; and/or the polyether blocks of the copolymer with polyamide blocks and with polyether blocks comprising ends of the amine chain are blocks of polyethylene glycol and/or of polytetrahydrofuran.
• the invention also relates to a method for preparing a composition, comprising the following steps:
• the mixture preferably in an extruder, of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends in the molten state and of at least one thermoplastic polyurethane in the molten state;
• composition has a tensile modulus at 23°C of less than or equal to 170 MPa.
• the invention also relates to a method for preparing a composition, comprising the following steps:
• thermoplastic polyurethane in the reactor in the presence of the copolymer with polyamide blocks and with polyether blocks comprising ends of the amine chain, so as to obtain a composition of thermoplastic polyurethane and of copolymer with polyamide blocks and with polyether blocks;
• composition in the form of granules or powder; wherein the composition has a tensile modulus at 23°C of less than or equal to 170 MPa.
• the invention also relates to an article consisting of, or comprising at least one element consisting of, a composition as described above, said article preferably being chosen from the soles of sports shoes, footballs or balls, gloves, personal protective equipment, rail pads, automotive parts, construction parts, optical equipment parts, electrical and electronic equipment parts, watch straps, toys, medical equipment parts such as catheters, transmission or transport belts, gears and conveyor belts for production lines.
• the invention also relates to a method of manufacturing an article as described above, comprising the following steps: - the supply of a composition as described above;
• the present invention makes it possible to meet the need expressed above. More particularly, it provides a low-density composition exhibiting both high elasticity and flexibility, low tensile settling and high tear strength and durability.
• thermoplastic polyurethane or TPU
• PEBA polyether blocks
• a reaction takes place between at least a part of the copolymer with polyamide blocks and with polyether blocks comprising ends of the amine chain and at least a part of the thermoplastic polyurethane, and more particularly between the amine functions of the copolymer with polyamide blocks and polyether blocks and the urethane functions of the thermoplastic polyurethane or the isocyanate functions present in the precursors of the thermoplastic polyurethane.
• This reaction between at least a part of the copolymer with polyamide blocks and with polyether blocks comprising amine chain ends and at least a part of the thermoplastic polyurethane allows better compatibility between these polymers. This results in an improvement of the properties of the alloys thus obtained, and in particular of the properties mentioned above.
• the invention relates to a composition
• a composition comprising at least one thermoplastic polyurethane and at least one copolymer with polyamide blocks and with polyether blocks having amine chain ends.
• end of chain and “end of chain” have the same meaning and can be used interchangeably.
• the PEBAs according to the invention have amine chain ends.
• the PEBAs according to the invention result from the polycondensation of polyamide blocks (rigid or hard blocks) with reactive ends with blocks polyethers (flexible or soft blocks) with reactive ends, in particular from the polycondensation of polyamide blocks at the ends of dicarboxylic chains with polyoxyalkylene blocks at the ends of diamine chains, obtained for example by cyanoethylation and hydrogenation of polyoxyalkylene a,w-dihydroxylated aliphatic blocks called polyetherdiols.
• the polyamide blocks with dicarboxylic chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.
• Three types of polyamide blocks can advantageously be used.
• the polyamide blocks come from the condensation of a dicarboxylic acid, in particular those having from 4 to 36 carbon atoms, preferably those having from 4 to 20 carbon atoms, more preferably from 6 to 18 carbon atoms. carbon, and an aliphatic or aromatic diamine, in particular those having 2 to 20 carbon atoms, preferably those having 6 to 14 carbon atoms.
• a dicarboxylic acid in particular those having from 4 to 36 carbon atoms, preferably those having from 4 to 20 carbon atoms, more preferably from 6 to 18 carbon atoms. carbon
• an aliphatic or aromatic diamine in particular those having 2 to 20 carbon atoms, preferably those having 6 to 14 carbon atoms.
• dicarboxylic acids mention may be made of 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acids and terephthalic and isophthalic acids, but also dimerized fatty acids .
• diamines examples include tetramethylene diamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, isomers of bis-(4-aminocyclohexyl)-methane (BACM), bis -(3-methyl-4- aminocyclohexyl)methane (BMACM), and 2-2-bis-(3-methyl-4- aminocyclohexyl)-propane (BMACP), para-amino-di-cyclo-hexyl-methane ( PACM), isophoronediamine (IPDA), 2,6-bis-(aminomethyl)-norbornane (BAMN) and piperazine (Pip).
• BCM bis-(4-aminocyclohexyl)-methane
• BMACM bis -(3-methyl-4- aminocyclohexyl)methane
• BMACP 2-2-bis
• polyamide blocks PA 4.12, PA 4.14, PA 4.18, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA 9.12, PA 10.10, PA 10.12, PA 10.14 and PA 10.18 are used.
• PA XY X represents the number of carbon atoms resulting from the diamine residues
• Y represents the number of carbon atoms resulting from the diacid residues, in a conventional manner.
• the polyamide blocks result from the condensation of one or more a,w-aminocarboxylic acids and/or of one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 with 18 carbon atoms or a diamine.
• lactams As examples of lactams, mention may be made of caprolactam, oenantholactam and lauryllactam. Mention may be made, as examples of ⁇ , ⁇ -amino carboxylic acid, of aminocaproic, amino-7-heptanoic, amino-10-decanoic, amino-11-undecanoic and amino-12-dodecanoic acids.
• the polyamide blocks of the second type are blocks of PA 10 (polydecanamide), PA 11 (polyundecanamide), of PA 12 (polydodecanamide) or of PA 6 (polycaprolactam).
• PA X notation, X represents the number of carbon atoms from amino acid residues.
• the polyamide blocks result from the condensation of at least one a,w-aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
• polyamide PA blocks are prepared by polycondensation:
• - comonomer(s) ⁇ Z ⁇ chosen from lactams and a,w-aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having X1 carbon atoms and at least one dicarboxylic acid having Y1 carbon atoms, (X1, Y1) being different from (X, Y),
• said ⁇ Z ⁇ comonomer(s) being introduced in a proportion by weight advantageously ranging up to 50%, preferably up to
• the dicarboxylic acid having Y carbon atoms is used as chain limiter, which is introduced in excess relative to the stoichiometry of the diamine(s).
• the polyamide blocks result from the condensation of at least two a,w-aminocarboxylic acids or of at least two lactams having from 6 to 12 carbon atoms or of a lactam and of a aminocarboxylic acid not having the same number of carbon atoms in the optional presence of a chain limiter.
• aliphatic ⁇ , ⁇ -aminocarboxylic acid mention may be made of aminocaproic, amino-7-heptanoic, amino-10-decanoic, amino-11-undecanoic and amino-12-dodecanoic acids.
• lactam mention may be made of caprolactam, oenantholactam and lauryllactam.
• aliphatic diamines mention may be made of hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.
• cycloaliphatic diacids mention may be made of 1,4-cyclohexyldicarboxylic acid.
• aliphatic diacids mention may be made of butane-dioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids, dimerized fatty acids.
• dimerized fatty acids preferably have a dimer content of at least 98%; preferably they are hydrogenated; these are, for example, products marketed under the "PRIPOL” brand by the "CRODA” company, or under the EMPOL brand by the BASF company, or under the Radiacid brand by the OLEON company, and polyoxyalkylene a,w-diacids .
• aromatic diacids mention may be made of terephthalic (T) and isophthalic (I) acids.
• cycloaliphatic diamines examples include the isomers of bis-(4-aminocyclohexyl)-methane (BACM), bis-(3-methyl-4-aminocyclohexyl)methane (BMACM) and 2-2-bis- (3-methyl-4-aminocyclohexyl)-propane (BMACP), and para-amino-di-cyclo-hexyl-methane (PACM).
• BMACM bis-(4-aminocyclohexyl)-methane
• BMACM bis-(3-methyl-4-aminocyclohexyl)methane
• BMACP 2-2-bis- (3-methyl-4-aminocyclohexyl)-propane
• PAM para-amino-di-cyclo-hexyl-methane
• IPDA isophoronediamine
• BAMN 2,6-bis-(aminomethyl)-norbornan
• PA X/Y, PA X/Y/Z, etc. refer to copolyamides in which X, Y, Z, etc. represent homopolyamide units as described above.
• the polyamide blocks of the copolymer used in the invention comprise polyamide blocks PA 6, PA 10, PA 11, PA 12, PA 5.4, PA 5.9, PA 5.10, PA 5.12, PA 5.13, PA 5.14, PA 5.16, PA 5.18, PA 5.36, PA 6.4, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 6.13, PA 6.14, PA 6.16, PA 6.18, PA 6.36, PA 10.4, PA 10.9, PA 10.10, PA 10.12, PA 10.13, or mixtures or copolymers thereof; and preferably comprise blocks of polyamide PA 6, PA 10, PA 11, PA 12, PA 6.10, PA 6.12, PA 10.10, PA 10.12, or mixtures or copolymers thereof, more preferably blocks of polyamide PA 11 , PA 12, PA 6, PA 6.12, or mixtures or copolymers thereof.
• the polyether blocks consist of alkylene oxide units.
• the polyether blocks may in particular be PEG (polyethylene glycol) blocks, i.e. consisting of ethylene oxide units, and/or PPG (propylene glycol) blocks, i.e. consisting of propylene oxide units, and/ or P03G (polytrimethylene glycol) blocks, that is to say consisting of polytrimethylene glycol ether units, and/or PTMG blocks, that is to say consisting of tetramethylene glycol units also called polytetrahydrofuran.
• the PEBA copolymers can comprise in their chain several types of polyethers, the copolyethers possibly being block or random.
• the polyether blocks can also consist of ethoxylated primary amines.
• ethoxylated primary amines By way of example of ethoxylated primary amines, mention may be made of the products of formula: in which m and n are integers between 1 and 20 and x an integer between 8 and 18. These products are for example commercially available under the brand NORAMOX® from the company CECA and under the brand GENAMIN® from the company CLARIFYING.
• the flexible polyether blocks according to the invention comprise polyoxyalkylene blocks with ends of Nhte chains, such blocks being able to be obtained by cyanoacetylation of polyoxyalkylene a,w-dihydroxylated aliphatic blocks called polyetherdiols.
• polyetherdiols More particularly, the commercial products Jeffamine or Elastamine can be used (for example Jeffamine®
• the polyetherdiol blocks are thus aminated to be transformed into polyether diamines and condensed with polyamide blocks with carboxylic ends.
• the general method for preparing PEBA copolymers having amide bonds between the PA blocks and the PE blocks is known and described, for example in the document EP 1482011.
• the polyether blocks can also be mixed with polyamide precursors and a chain limiter diacid to prepare polymers with polyamide blocks and polyether blocks having randomly distributed units (one-step process).
• Polyether diols with OH chain ends can be present with the amino polyether diols during their condensation with the polyamide blocks.
• These polyetherdiols with OH chain ends can be condensed with polyamide blocks with carboxylic ends, forming ester bonds between the PA blocks and the PE blocks (the products obtained being polyetheresteramides).
• PEBA in the present description of the invention relates both to PEBAX® marketed by Arkema, to Vestamid® marketed by Evonik®, to Grilamid® marketed by EMS, and to Pelestat® type PEBA marketed by Sanyo or any other PEBA from other providers.
• block copolymers described above 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 chosen from those described in the present description. , provided that these blocks comprise at least polyamide and polyether blocks.
• the copolymer according to the invention can be a segmented block copolymer comprising three different types of blocks (or “triblock”), which results from the condensation of several of the blocks described above.
• Said triblock can for example be 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, for example a PEG block and a PTMG block.
• the triblock is preferably a copolyetheresteramide.
• PEBA copolymers in the context of the invention are copolymers comprising blocks: PA 10 and PEG; PA 10 and PTMG; PA 11 and PEG; PA 11 and PTMG; PA12 and PEG; PA 12 and PTMG; PA 6.10 and PEG; PA 6.10 and PTMG; PA 6 and PEG; PA 6 and PTMG; PA 6.12 and PEG; PA 6.12 and PTMG.
• the number-average molar mass of the polyamide blocks in the PEBA copolymer is preferably from 400 to 20,000 g/mol, more preferably from 500 to 10,000 g/mol.
• the number-average molar mass of the polyamide blocks in the PEBA copolymer is from 400 to 500 g/mol, or 500 to 600 g/mol, or from 600 to 1000 g/mol, or from 1000 to 1500 g/mol, or from 1500 to 2000 g/mol, or from 2000 to 2500 g/mol, or from 2500 to 3000 g/mol, or from 3000 to 3500 g/mol, or from 3500 to 4000 g/mol, or from 4000 to 5000 g/mol, or from 5000 to 6000 g/mol, or from 6000 to 7000 g/mol, or from 7000 to 8000 g/mol, or from 8000 to 9000 g/mol, or from 9000 to 10000 g /mol, or from 10000 to 11000 g/mol, or from
• the number-average molar mass of the polyether blocks is preferably from 100 to 6000 g/mol, more preferably from 200 to 3000 g/mol. In some embodiments, the number average molar mass of the polyether blocks is from 100 to 200 g/mol, or from 200 to 500 g/mol, or from 500 to 800 g/mol, or from 800 to 1000 g/mol , or from 1000 to 1500 g/mol, or from 1500 to 2000 g/mol, or from 2000 to 2500 g/mol, or from 2500 to 3000 g/mol, or from 3000 to 3500 g/mol, or from 3500 to 4000 g/mol, or from 4000 to 4500 g/mol, or from 4500 to 5000 g/mol, or from 5000 to 5500 g/mol, or from 5500 to 6000 g/mol.
• the number-average molar mass is fixed by the content of chain limiter. It can be calculated according to the relationship:
• Mn nmonomer X MWrepeat pattern / nistring mimic + MWstring limiter
• nmonomer represents the number of moles of monomer
• nchain limiter represents the number of moles of excess diacid limiter
• MWrepeat unit represents the molar mass of the repeat unit
• MWchain limiter represents the molar mass of the diacid in excess.
• the number-average molar mass of the polyamide blocks and of the polyether blocks can be measured before the copolymerization of the blocks by gel permeation chromatography (GPC).
• the mass ratio of the polyamide blocks relative to the polyether blocks of the copolymer is from 0.1 to 20, preferably from 0.5 to 18 even more preferentially from 0.6 to 15.
• This mass 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.
• the mass ratio of the polyamide blocks relative to the polyether blocks of the copolymer can be from 0.1 to 0.2, or from 0.2 to 0.3, or from 0.3 to 0.4, or from 0 .4 to 0.5, or 0.5 to 0.6, or 0.6 to 0.7, or 0.7 to 0.8, or 0.8 to 0.9, or 0 .9 to 1, or 1 to 1.5, or 1.5 to 2, or 2 to 2.5, or 2.5 to 3, or 3 to 3.5, or 3.5 to 4, or 4 to 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 from 19 to 20.
• the copolymer used in the invention has a Shore D hardness greater than or equal to 30.
• the copolymer used in the invention has an instantaneous hardness of 65 Shore A to 80 Shore D, more preferably of 75 Shore A to 65 Shore D, more preferably from 80 Shore A to 55 Shore D.
• the hardness measurements can be carried out according to standard ISO 7619-1.
• the PEBA according to the invention has a concentration according to Nhted of 0.01 meq/g to 1 meq/g, preferably of 0.02 meq/g to 0.4 meq/g.
• PEBA can have a concentration depending on Nhtede 0.01 to 0.015 meq/g, or 0.015 to 0.02 meq/g, or 0.02 to 0.025 meq/g, or 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 0.06 to 0.07 meq/g, or 0.07 to 0.08 meq/g, or 0.08 to 0.09 meq/g, or 0 0.09 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
• Concentration as a function of Nhte can be measured using a potentiometric assay.
• This assay can for example be carried out as follows: the PEBAs are first dissolved in m-cresol at 80° C. then the terminal NH2 functions are assayed with a solution of perchloric acid.
• the PEBA according to the invention may have a COOH function concentration of 0.002 meq/g to 0.2 meq/g, preferably of 0.005 meq/g to 0.1 meq/g, more preferably of 0.01 meq/ g to 0.08 meq/g.
• the PEBA according to the invention may have a COOH function concentration of 0.002 to 0.005 meq/g, or 0.005 to 0.01 meq/g, or 0.01 to 0.02 meq/g, or 0.02 to 0.03 meq/g, or 0.03 to 0.04 meq/g, or 0.04 to 0.05 meq/g, or 0.05 to 0.06 meq/g, or 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 0.09 to 0.1 meq/g, or 0.15 to 0.2 meq/g.
• the COOH-based concentration can be determined by potentiometric analysis.
• the PEBA according to the invention may comprise hydroxyl (OH) chain ends (coming for example from the condensation of polyetherdiols with OH chain ends with polyamide blocks with carboxylic ends).
• the PEBA according to the invention can have a concentration in OH function (that is to say in hydroxyl chain ends) of 0.002 to 0.2 meq/g, preferably of 0.005 to 0.05 meq/ g.
• the OH function concentration can be determined by proton NMR.
• a measurement protocol is detailed in the article “Synthesis and characterization of poly(copolyethers-block-polyamides) - II. Characterization and properties of the multiblock copolymers”, Maréchal etal., Polymer, Volume 41, 2000, 3561-3580.
• TPU Thermoplastic Polyurethane
• thermoplastic polyurethane according to the invention is a copolymer with rigid blocks and with flexible blocks.
• the term "rigid block” means a block which has a melting point.
• the presence of a melting point can be determined by differential scanning calorimetry, according to ISO 11357-3 Plastics - Differential scanning calorimetry (DSC) Part 3 standard. vitreous (Tg) less than or equal to 0°C.
• the glass transition temperature can be determined by differential scanning calorimetry, according to standard ISO 11357-2 Plastics - Differential scanning calorimetry (DSC) Part 2.
• Thermoplastic polyurethanes result from the reaction of at least one polyisocyanate with at least one compound reactive with isocyanate, preferably having two functional groups reactive with isocyanate, more preferably a polyol, and optionally with a chain extender, optionally in the presence of a catalyst.
• the rigid blocks of TPU are blocks made up of units derived from polyisocyanates and chain extenders while the flexible blocks mainly comprise units derived from compounds reactive with isocyanate having a molar mass between 0.5 and 100 kg/ mol, preferably polyols.
• the polyisocyanate can be aliphatic, cycloaliphatic, araliphatic and/or aromatic.
• the polyisocyanate is a diisocyanate.
• the polyisocyanate is chosen from the group consisting of tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl- butylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 2,4-paraphenylene diisocyanate (PPDI), 2,4-tetramethylene xylene diisocyanate (TMXDI), 4 ,4'-, 2,4'-,
• the polyisocyanate is selected from the group consisting of diphenylmethane diisocyanates (MDI), toluene diisocyanates (TDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), methylene bis (4-cyclohexyl isocyanate) (HMDI) and mixtures thereof.
• MDI diphenylmethane diisocyanates
• TDI toluene diisocyanates
• PDI pentamethylene diisocyanate
• HDI hexamethylene diisocyanate
• HMDI methylene bis (4-cyclohexyl isocyanate
• the polyisocyanate is 4,4'-MDI (4,4'-diphenylmethane diisocyanate), 1,6-HDI (1,6-hexamethylene diisocyanate) or a mixture of these.
• the compound(s) reactive with the isocyanate 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 compound or compounds reactive with the isocyanate corresponds to the number of functions reactive with the isocyanate of the molecules, calculated theoretically for a molecule from a quantity of compounds.
• the isocyanate-reactive compound has, statistically averaged, a Zerewitinoff active hydrogen number within the above ranges.
• the isocyanate-reactive compound (preferably a polyol) has a number average molar mass of 500 to 100,000 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 from 800 to 4000 g/mol.
• the isocyanate-reactive compound has a number average 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 from 3500 to 4000 g/mol, or from 4000 to 5000 g/mol, or from 5000 to 6000 g/mol, or from 6000 to 7000 g/mol, or from 7000 to 8000 g/mol, or from 8000 to 10000 g/mol, or from 10000 to 15000 g/mol, or from 15000 to 20000 g
• the isocyanate-reactive compound has at least one reactive group selected from hydroxyl group, amine group, thiol group and carboxylic acid group.
• the isocyanate-reactive compound has at least one reactive hydroxyl group, more preferably several hydroxyl groups.
• the compound reactive with the isocyanate comprises or consists of a polyol.
• 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, such 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 being a polyether polyol and/or a polyester polyol).
• polyester polyol mention may be made of polycaprolactone polyols and/or copolyesters based on one or more carboxylic acids chosen from adipic acid, succinic acid, pentanedioic acid and/or sebacic acid and one or more alcohols chosen from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1, 6-hexanediol and/or polytetrahydrofuran.
• carboxylic acids chosen from adipic acid, succinic acid, pentanedioic acid and/or sebacic acid and one or more alcohols chosen from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol,
• the copolyester can be based on adipic acid and a mixture of 1,2-ethanediol and 1,4-butanediol, or the copolyester can be based on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof, and polytetrahydrofuran (tetramethylene glycol), or the copolyester may be a mixture of these copolyesters.
• polyether polyol polyether diols (i.e. aliphatic ⁇ , ⁇ -dihydroxylated polyoxyalkylene blocks) are preferably used.
• the polyether polyol is a polyetherdiol based on ethylene oxide, propylene oxide, and/or butylene oxide, a block copolymer based on ethylene oxide and propylene, a polyethylene glycol, a polypropylene glycol, a polybutylene glycol, a polytetrahydrofuran, a polybutane diol or a mixture thereof.
• the polyether polyol is preferably a polytetrahydrofuran (flexible blocks of thermoplastic polyurethane therefore being blocks of polytetrahydrofuran) and/or a polypropylene glycol (flexible blocks of thermoplastic polyurethane therefore being blocks of polypropylene glycol) and/or a polyethylene glycol ( flexible blocks of thermoplastic polyurethane therefore being blocks of polyethylene glycol), preferably a polytetrahydrofuran having a number-average molar mass of 500 to 15,000 g/mol, preferably of 1,000 to 3,000 g/mol.
• the polyether polyol can be a polyetherdiol which is the reaction product of ethylene oxide and propylene oxide; the molar ratio of ethylene oxide to propylene oxide is preferably 0.01 to 100, more preferably 0.1 to 9, more preferably 0.25 to 4, more preferably 0 .4 to 2.5, more preferably from 0.6 to 1.5 and it is more preferably 1.
• the polysiloxane diols which can be used in the invention preferably have a number-average molar mass of 500 to 15,000 g/mol, preferably of 1,000 to 3,000 g/mol.
• the number average molar mass can be determined by GPC, preferably according to standard ISO 16014-1:2012.
• the polysiloxane diol is a polysiloxane of formula (I): [Chem. 2]
• R is preferably C2-C4 alkylene
• R' is preferably C1-C4 alkyl
• each of n, m and p independently represent an integer preferably between 0 and 50, m more preferably being 1 to 50, even more preferably from 2 to 50.
• the polysiloxane has the following formula (II):
• the polyalkylene diols which can be used in the invention are preferably based on butadiene.
• the polycarbonate diols which can be used in the invention are preferably aliphatic polycarbonate diols.
• the polycarbonate diol is preferably based on an alkanediol. Preferably, it is strictly bifunctional.
• the preferred polycarbonate diols according to the invention are those based on butanediol, pentanediol and/or hexanediol, in particular 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane -(1,5)-diol, or mixtures thereof, more preferably based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or mixtures thereof.
• the polycarbonate diol can be a polycarbonate diol based on butanediol and hexanediol, or based on pentanediol and hexanediol, or based on hexanediol, or can be a mixture of two or more of these polycarbonate diols .
• the polycarbonate diol advantageously has a number-average molar mass of 500 to 4000 g/mol, preferably of 650 to 3500 g/mol, more preferably of 800 to 3000 g/mol.
• the number average molar mass can be determined by GPC, preferably according to standard ISO 16014-1:2012.
• One or more polyols can be used as the isocyanate-reactive compound.
• the flexible blocks of the TPU are blocks of polytetrahydrofuran, of polypropylene glycol and/or of polyethylene glycol.
• a chain extender is used for the preparation of the thermoplastic polyurethane, in addition to the isocyanate and the compound reactive with the isocyanate.
• the chain extender can be 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 ISO 16014-1:2012.
• the chain extender preferably has two isocyanate-reactive groups (also called "functional groups"). A single chain extender or a mixture of two or more chain extenders can be used.
• the chain extender is preferably bifunctional.
• chain extenders are diamines and alkanediols with 2 to 10 carbon atoms.
• the chain extender can be chosen 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-dimethanol cyclohexane, neopentylglycol, hydroquinone bis (beta-hydroxyethyl ) ether (HQEE), di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and/or deca-alkylene glycol, their respective oli
• 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 of these, and more preferably it is chosen from 1,3-propanediol, 1,4-butanediol and/or 1,6-hexanediol. Even more preferably, the chain extender is a mixture of 1,4-butanediol and 1,6-hexanediol, more preferably in a molar ratio of 6:1 to 10:1.
• a catalyst is used to synthesize the thermoplastic polyurethane.
• the catalyst makes it possible to accelerate the reaction between the NCO groups of the polyisocyanate and the compound reactive with the isocyanate (preferably with the hydroxyl groups of the compound reactive with the isocyanate) and, if present, with the extender of chain.
• the catalyst is preferably a tertiary amine, more preferably chosen from triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)-ethanol and/or diazabicyclo-(2,2 ,2)-octane.
• the catalyst is an organic metal compound such as a titanium acid ester, an iron compound, preferably ferric acetylacetonate, a tin compound, preferably those of carboxylic acids, more preferably tin diacetate, tin dioctoate, tin dilaurate or dialkyl tin salts, preferably dibutyl tin diacetate and/or dibutyl tin dilaurate, an acid salt bismuth carboxylic acid, preferably bismuth decanoate, or a mixture thereof.
• organic metal compound such as a titanium acid ester, an iron compound, preferably ferric acetylacetonate, a tin compound, preferably those of carboxylic acids, more preferably tin diacetate, tin dioctoate, tin dilaurate or dialkyl tin salts, preferably dibutyl tin diacetate and/or dibutyl tin dilaurate, an
• the catalyst is selected from the group consisting of tin dioctoate, bismuth decanoate, titanium acid esters and mixtures thereof. More preferably, the catalyst is tin dioctoate.
• the molar ratios of the compound reactive with the isocyanate and of the chain extender can be varied to adjust the hardness and the melt index of the TPU. Indeed, when the proportion of chain extender increases, the hardness and melt viscosity of the TPU increases while the melt index of the TPU decreases.
• the compound reactive with the isocyanate and the chain extender can be used in a molar ratio of 1: 1 to 1:5, preferably from 1:1.5 to 1:4.5, preferably so that the mixture of isocyanate-reactive compound and chain extender has an equivalent weight of hydroxyl greater than 200, more particularly 230 to 650, even more preferably 230 to 500.
• the isocyanate-reactive compound and the chain extender can be used in a molar ratio of 1:5.5 to 1:15, preferably 1:6 to 1:12, preferably so as to that the mixture of isocyanate-reactive compound and chain extender has a hydroxyl equivalent weight of 110 to 200, more preferably ntially from 120 to 180.
• the polyisocyanate, the compound reactive with the isocyanate, and preferably the chain extender are reacted, preferably in the presence of a catalyst, in quantities such that the ratio in equivalent of the NCO groups of the polyisocyanate relative to the sum of the hydroxyl groups of the isocyanate-reactive compound and the chain extender is 0.95:1 to 1.10:1, preferably 0.98:1 to 1.08:1, more preferably from 1:1 to 1.05:1.
• the catalyst is advantageously present in an amount of 0.0001 to 0.1 parts by weight per 100 parts by weight of the TPU synthesis reagents.
• the TPU according to the invention preferably has a weight-average molar mass greater than or equal to 10,000 g/mol, preferably greater than or equal to 40,000 g/mol and more preferably greater than or equal to 60,000 g/mol.
• the weight-average molar mass of the TPU is less than or equal to 80,000 g/mol.
• Weight average molar masses can be determined by gel permeation chromatography (GPC).
• the TPU is semi-crystalline. Its melting point 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 ISO 11357-3 Plastics - Differential scanning calorimetry (DSC) Part 3.
• the TPU can be a recycled TPU and/or a partially or completely biobased TPU.
• the TPU has a Shore D hardness of less than or equal to 75, more preferably less than or equal to 65.
• the TPU used in the invention may have a hardness of 65 Shore A to 70 Shore D, preferably of 75 Shore A to 60 Shore D. Hardness measurements can be performed according to ISO 7619-1.
• the TPU according to the invention has an OH function concentration of 0.002 meq/g to 0.6 meq/g, preferably of 0.01 meq/g to 0.4 meq/g, more preferably of 0 .03 meq/g to 0.2 meq/g.
• the TPU according to the invention has an OH function concentration of 0.002 to 0.005 meq/g, or 0.005 to 0.01 meq/g, or 0.01 to 0.02 meq/g, or 0.02 to 0.04 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.
• the OH function concentration can be determined by NMR by following the conditions described in the article below: "Reactivity of isocyanates with urethanes: Conditions for allophanate formation", Lapprand et al., Polymer Degradation and Stability, Volume 90, N °2, 2005, 363-373.
• composition according to the invention is an alloy comprising at least one PEBA and at least one TPU.
• alloy we mean a homogeneous mixture (macroscopically, i.e. to the naked eye).
• the composition according to the invention advantageously comprises from 20 to 95% by weight of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends, and from 5 to 80% by weight of at least one thermoplastic polyurethane , more preferably from 30 to 85% by weight of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends, and from 15 to 70% by weight of at least one thermoplastic polyurethane, even more preferably from 40 to 80% by weight of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends, and from 20 to 60% by weight of at least one thermoplastic polyurethane, relative to the total weight of the composition.
• the composition comprises from 20 to 30% by weight of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends, and from 70 to 80% by weight of at least one polyurethane thermoplastic, or from 30 to 40% by weight of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends, and from 60 to 70% by weight of at least one thermoplastic polyurethane, or from 40 to 50% by weight of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends, and from 50 to 60% by weight of at least one thermoplastic polyurethane, or from 50 to 60% by weight of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends, and from 40 to 50% by weight of at least one thermoplastic polyurethane, or from 60 to 70% by weight of at least one block copolymer polyamides and with polyether blocks comprising amine chain ends, and from 30 to 40% in poi ds of at least one thermoplastic polyurethane
• the molar ratio of the urethane functions to the amine functions Nhte of the assembly consisting of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends and at least one thermoplastic polyurethane, in the composition according to the invention can be from 15 to 350, preferably from 25 to 250, even more preferably from 40 to 200.
• concentrations of amine function and urethane function can be determined by NMR by following the conditions described in the article below : “Reactivity of isocyanates with urethanes: Conditions for allophanate formation”, Lapprand et al., Polymer Degradation and Stability, Volume 90, N°2, 2005, 363-373.
• composition according to the invention may consist of at least one copolymer with polyamide blocks and with polyether blocks comprising ends of the amine chain and of at least one thermoplastic polyurethane.
• the composition may comprise one or more additives, preferably chosen from impact modifiers, functional or non-functional polyolefins, copolyetheresters, copolymers of ethylene and vinyl acetate, copolymers of ethylene and acrylate, copolymers of ethylene and alkyl(meth)acrylate, copolymers comprising ethylene and styrene, polyorganosiloxanes, plasticizers, nucleating agents, lubricating agents, mold release agents, dyes, pigments, fillers organic or inorganic, reinforcing agents, flame retardants, UV absorbers, optical brighteners, light stabilizers, antioxidants and mixtures thereof.
• 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.
• 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 at 23° C. of the composition is less than or equal to 150 MPa.
• it may be 20 to 30 MPa, or 30 to 40 MPa, or 40 to 50 MPa, or 50 to 60 MPa, or 60 to 70 MPa, or 70 to 80 MPa, or 80 at 90 MPa, or from 90 to 100 MPa, or from 100 to 110 MPa, or from 110 to 120 MPa, or from 120 to 130 MPa, or from 130 to 140 MPa, or from 140 to 150 MPa, or from 150 to 160 MPa, or 160 to 170 MPa.
• the quantity by mass of total flexible blocks is from 10 to 95%, more preferentially from 30 to 90%, even more preferentially from 50 to 85 %, relative to the total weight of PEBA and TPU.
• the quantity by mass of total flexible blocks may in particular be, relative to the total weight of the PEBA and the TPU, from 10 to 20%, or from 20 to 30%, or from 30 to 40%, or from 40 to 50%, or from 50 to 60%, or from 60 to 70%, or from 70 to 80%, or from 80 to 90%, or from 90 to 95%.
• the mass quantity of total soft blocks can be determined by nuclear magnetic resonance (NMR).
• the composition has a tan d at 23° C. of less than or equal to 0.12, preferably less than or equal to 0.11, advantageously less than or equal to 0.10.
• the tan d (or loss factor) at 23°C corresponds to the ratio of the loss modulus E” to the modulus of elasticity E' measured at a temperature of 23°C by dynamic mechanical analysis (DMA). It can be measured according to the ISO 6721 standard dating from 2019, the measurement being carried out at a deformation of 0.1% in tension, at a frequency of 1 Hz, and at a heating rate of 2°C/min.
• DMA dynamic mechanical analysis
• the tan d at 23°C of the composition can be 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.
• the composition according to the invention preferably has a density less than or equal to 1.16, more preferably less than or equal to 1.14, advantageously less than or equal to 1.12.
• the density of the composition can be determined according to the ISO 1183-1 standard.
• the composition may have a specific gravity 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 from 1.04 to 1.05, or from 1.05 to
• the composition preferably has a Shore A hardness of 70 to 98, more preferably of 75 to 95.
• the hardness measurements can be carried out according to standard ISO 7619-1.
• composition may advantageously have a permanent tensile deformation after 10 cycles of deformation at 30% less than or equal to 15%, preferably less than or equal to 13%.
• Tensile set can be determined as shown below in the "Examples" section.
• composition is advantageously in the form of granules. Alternatively, it may be in powder form.
• composition of TPU and PEBA according to the invention comprises at least one part of copolymer with polyamide blocks and with polyether blocks covalently bonded to at least one part of thermoplastic polyether by a urea function.
• the composition according to the invention has a concentration of urea function from 0.001 meq/g to 0.1 meq/g, preferably from 0.003 meq/g to 0.08 meq/g, more preferably from 0.005 meq/ g at 0.05. meq/g.
• concentration according to urea function can be determined by NMR by following the conditions described in the article below: "Reactivity of isocyanates with urethanes: Conditions for allophanate formation”, Lapprand et al., Polymer Degradation and Stability, Volume 90, N°2, 2005, 363-373.
• the part of the copolymer with polyamide blocks and with polyether blocks covalently bonded to at least a part of the thermoplastic polyurethane by a urea function represents 10% or less by weight, more preferably 5% or less by weight, preferably further 3% or less by weight, more preferably 2% or less by weight, of the amount of copolymer containing polyamide blocks and polyether blocks.
• the invention relates to a composition obtained by the reaction of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends, and at least one thermoplastic polyurethane or thermoplastic polyurethane precursors.
• the features described above may similarly apply to this aspect of the invention.
• the amounts in the composition of at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends and of the at least one thermoplastic polyurethane described above can apply, respectively, to the amount of at least at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends and the amount of at least one thermoplastic polyurethane or thermoplastic polyurethane precursors reacted.
• the composition has a tensile modulus at 23° C. of less than or equal to 170 MPa.
• the invention also relates to a method of preparing a composition as described above.
• the composition according to the invention can be prepared by a process comprising a step of mixing at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends in the molten state and at least one thermoplastic polyurethane in the molten state.
• a preparation process allows, under certain conditions of temperature and mixing time, a reaction to take place between the amine functions of a part of the copolymer with polyamide blocks and with polyether blocks and the urethane functions of the TPU, which improves the compatibility between the polyamide block and polyether block copolymer and the thermoplastic polyurethane.
• the quantity of copolymer with polyamide blocks and with polyether blocks comprising amine chain ends in the molten state mixed is 20 to 95 wt%, preferably 30 to 85 wt%, more preferably 40 to 80 wt%, and the amount of melt thermoplastic polyurethane mixed is 5 to 80 wt% , preferably from 15 to 70% by weight, more preferably from 20 to 60% by weight, relative to the total weight of the composition.
• the mixing can take place in any device for mixing, kneading or extruding plastic materials in the molten state known to those skilled in the art, such as an internal mixer, a roller mixer, an extruder, such as a single-screw extruder or a contra- or co-rotating twin-screw extruder, a co-kneader, such as a continuous co-kneader, or a stirred reactor.
• the mixing takes place in an extruder or a co-kneader, more preferably in an extruder, even more preferably in a twin-screw extruder.
• the mixing is carried out at a temperature greater than or equal to 160°C, preferably from 160 to 300°C, more preferably from 180 to 260°C.
• 160°C preferably from 160 to 300°C, more preferably from 180 to 260°C.
• the mixing is carried out for a period of 30 seconds to 15 minutes, preferably 40 seconds to 10 minutes.
• the mixing is carried out with stirring.
• the copolymer with polyamide blocks and with polyether blocks comprising amine chain ends and the thermoplastic polyurethane can independently be, before their mixing in the molten state, in the form of powder or granules.
• the mixing step may comprise mixing the copolymer with polyamide blocks and with polyether blocks comprising amine chain ends and thermoplastic polyurethane, in the molten state, with other constituents of the composition (for example the additives).
• the preparation process comprises a step of shaping the mixture in the form of granules or powder.
• the mixture When the mixture is put into the form of a powder, it is preferably first put into the form of 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.
• the mixture is put in the form of granules.
• the composition can be prepared by introducing at least one copolymer with polyamide blocks and with polyether blocks comprising amine chain ends during the synthesis of at least one thermoplastic polyurethane.
• the copolymer with polyamide blocks and with polyether blocks comprising amine chain ends is used as a compound reactive with isocyanate (as described above in the section "Thermoplastic polyurethane (TPU)" ), optionally in addition to another isocyanate-reactive compound, preferably a polyol as described above, and/or a chain extender as described above.
• the preparation process may include the steps of:
• thermoplastic polyurethane precursors that is to say at least one polyisocyanate, optionally at least one compound reactive with isocyanate and optionally at least one chain extender;
• thermoplastic polyurethane in the reactor in the presence of the copolymer with polyamide blocks and with polyether blocks comprising ends of the amine chain, so as to obtain a composition of thermoplastic polyurethane and of copolymer with polyamide blocks and with polyether blocks.
• Such a preparation process allows the reaction of part of the amine functions NH2 of the copolymer with polyamide blocks and with polyether blocks with the isocyanate functions of part of the polyisocyanate during the synthesis of the thermoplastic polyurethane, leading to the formation of covalent bonds. between the copolymer with polyamide blocks and with polyether blocks and the thermoplastic polyurethane, which improves the compatibility between the copolymer with polyamide blocks and with polyether blocks and the thermoplastic polyurethane.
• the quantity of copolymer with polyamide blocks and with polyether blocks comprising amine chain ends introduced into the reactor is from 20 to 95% by weight, preferably from 30 to 85% by weight, more preferably from 40 to 80 % by weight, and the amount of thermoplastic polyurethane precursors introduced into the reactor is from 5 to 80% by weight, preferably from 15 to 70% by weight, more preferably from 20 to 60% by weight, relative to the total weight of the composition.
• the steps of introducing the precursors of the thermoplastic polyurethane and of introducing the copolymer with polyamide blocks and with polyether blocks comprising amine chain ends can be simultaneous or carried out in any order.
• a catalyst, in particular as described above, can also be introduced into the reactor.
• the reactor can be a batch reactor, an agitated reactor, a static mixer, an internal mixer, a roller mixer, an extruder, such as a single-screw extruder or a contra- or co-rotating twin-screw extruder, a continuous co-kneader , or a combination thereof.
• the reactor is an extruder, more preferably a twin-screw extruder.
• the thermoplastic polyurethane synthesis step (in the presence of the copolymer with polyamide blocks and with polyether blocks comprising amine chain ends) is carried out at a temperature greater than or equal to 160° C., preferably from 160 to 300° C. C, more preferably 180 to 270°C. These temperature ranges allow an optimal reaction between the copolymer with polyamide blocks and with polyether blocks comprising amine chain ends and the thermoplastic polyurethane, and therefore better compatibility of the two polymers.
• the process may comprise the introduction into the reactor of one or more additives, and their mixing with the thermoplastic polyurethane and the copolymer with polyamide blocks and with polyether blocks comprising amine chain ends in the reactor.
• the preparation process comprises a step of shaping the composition in the form of granules or powder, more preferably in the form of granules.
• the composition can be put in the form of a powder in the manner described above in relation to the first variant of the method of preparation.
• the invention also relates to a composition obtained by, or capable of being obtained by, a preparation process as described above.
• a composition obtained by, or capable of being obtained by, a preparation process as described above The characteristics described above, particularly in the “Composition of TPU and PEBA” section, can be applied in a similar way to this composition.
• composition according to the invention can be used to manufacture sports equipment, such as the soles of sports shoes, ski boots, intermediate soles, insoles, or even functional components of soles, in the form of inserts in different parts of the sole (heel or arch for example), or even components of shoe uppers in the form of reinforcements or inserts in the structure of the shoe upper, in the form of protections.
• sports equipment such as the soles of sports shoes, ski boots, intermediate soles, insoles, or even functional components of soles, in the form of inserts in different parts of the sole (heel or arch for example), or even components of shoe uppers in the form of reinforcements or inserts in the structure of the shoe upper, in the form of protections.
• balls can also be used to manufacture balls, sports gloves (for example football gloves), golf ball components, rackets, protective elements (vests, interior elements of helmets, hulls, etc.). ).
• composition according to the invention can also be used for the manufacture of various parts:
• compositions of the invention have a soft-silky feel, adhere well to polyamide and more specifically to transparent polyamide by overmoulding, and are resistant to sebum;
• compositions of the invention have a soft touch, good haptic properties, adhere perfectly by overmoulding, are resistant to sebum and resistant to abrasion;
• compositions of the invention are heat-resistant, abrasion-resistant, and easy to implement by overmoulding;
• Articles or elements consisting of a composition as described above can be manufactured by injection molding.
• TPU with rigid blocks based on 4,4'-MDI and 1,6-HDO (1,6-hexanediol) and with flexible polyester blocks based on adipic acid and butane diol, 95 Shore A hardness.
• TPU with rigid blocks based on 4,4'-MDI and 1,6-HDO (1,6-hexanediol) and with flexible polyester blocks based on adipic acid and butane diol, 59 Shore D hardness.
• PEBA copolymer comprising ends of the amine chain, comprising rigid blocks of polyamide 11 and flexible blocks of polyether (copolymer of PTMG and PPG) comprising ends of the amine chain, the rigid blocks of polyamide 11 with an average molar mass of number 1000 g/mol, and the flexible blocks of polyether with a number-average molar mass of 1000 g/mol, the PEBA copolymer having a concentration according to NH2 of 0.032 meq/g.
• compositions above were manufactured 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.
• compositions were then dried under reduced pressure at 80° C. in order to reach a moisture content of less than 0.04%.
• compositions No. 1 and No. 2 are compositions according to the invention, composition No. 3 is a comparative composition.
• compositions according to the invention have a lower tensile set than the comparative composition: a part made up of such compositions will have a greater durability than a part made up of the comparative composition.
• compositions according to the invention have a loss factor (tan d) at 23° C. lower than that of the comparative composition, and therefore have a higher elasticity than the comparative composition, while maintaining a low density.

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• 2021
  • 2021-04-22 FR FR2104203A patent/FR3122182B1/fr active Active
• 2022
  • 2022-04-22 US US18/556,037 patent/US20240240018A1/en active Pending
  • 2022-04-22 WO PCT/FR2022/050771 patent/WO2022223936A1/fr active Application Filing
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