Branched hard- and soft- block copolymers

Abstract

To provide polymers enabling the formation of foams having one or more advantageous properties from among: a low density; a low compression set; a high fatigue strength in compression; and good resilience properties.SOLUTION: The invention concerns a branched hard- and soft- block copolymer, in which the branchings are provided by a polyol residue binding hard blocks of the copolymer, the polyol being a polyol comprising at least three hydroxyl groups, the copolymer having a weight average molar mass Mw of 80,000 g / mol or more, and in which the ratio of the weight average molar mass Mw of the copolymer to the number average molar mass Mn of the copolymer is 2.2 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to copolymers containing rigid and flexible blocks and foams formed from the copolymers. [Background technology]

[0002] Various polymer foams are used, inter alia, in the field of sports equipment, such as shoe soles or sole components, gloves, rackets or golf balls, and personal protection items, especially when playing sports (jackets, helmet interiors, covers, etc.).

[0003] Such applications require a particular set of physical properties that ensure resilience, low compression set, and the ability to withstand repeated impacts without deformation and recover to their original shape.

[0004] Document CN 107325280 describes polyether / polyamide elastomers obtained by copolymerization of polyamides, polyethers and branching agents and which can be used to prepare foams.

[0005] Document WO 2018 / 087501 describes compositions comprising copolymers containing flexible and rigid blocks and polyols with more than two functional groups, and their use in extrusion processes, in particular for the production of moisture-permeable, waterproof films.

[0006] There is a need to provide polymers that allow for the formation of foams having one or more advantageous properties: low density; low compression set; high fatigue strength under compression; and good resilience. Summary of the Invention

[0007] The present invention first provides: A branched copolymer containing a rigid block and a flexible block, wherein the branches are created by polyol residues connecting the rigid blocks of the copolymer; the polyol is a polyol containing at least three hydroxyl groups; The copolymer relates to a branched copolymer containing a rigid block and a flexible block, having a weight average molecular weight Mw of 80,000 g / mol or more, and a ratio of the weight average molecular weight Mw of the copolymer to the number average molecular weight Mn of the copolymer of 2.2 or more.

[0008] According to one particular embodiment, the copolymer has a weight-average molecular weight Mw ranging from 80,000 to 300,000 g / mol, preferably from 85,000 to 200,000 g / mol and more preferentially from 90,000 to 175,000 g / mol.

[0009] According to one particular embodiment, the ratio of the weight average molecular weight Mw of the copolymer to the number average molecular weight Mn of the copolymer is greater than or equal to 2.4.

[0010] According to one particular embodiment, the ratio of the z-average molar mass Mz of the copolymer to the weight-average molecular weight Mw of the copolymer is greater than or equal to 1.8, preferably greater than or equal to 2.

[0011] According to one particular embodiment, the rigid blocks are selected from polyamide blocks, polyester blocks, polyurethane blocks and combinations thereof.

[0012] According to certain embodiments, the flexible blocks are selected from polyether blocks, polyester blocks, and combinations thereof.

[0013] According to one particular embodiment, the copolymer is a copolymer containing polyamide blocks and polyether blocks.

[0014] According to one particular embodiment, the polyamide blocks are selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 5.4, polyamide 5.9, polyamide 5.10, polyamide 5.12, polyamide 5.13, polyamide 5.14, polyamide 5.16, polyamide 5.18, polyamide 5.36, polyamide 6.4, polyamide 6.9, polyamide 6.10, polyamide 6.12, polyamide 6.13, polyamide 6.14, polyamide 6.16, polyamide 6.18, polyamide 6.36, polyamide 10.4, polyamide 10.9, polyamide 10.10, The polymers are selected from the group consisting of polyamide 10.12, polyamide 10.13, polyamide 10.14, polyamide 10.16, polyamide 10.18, polyamide 10.36, polyamide 10.T, polyamide 12.4, polyamide 12.9, polyamide 12.10, polyamide 12.12, polyamide 12.13, polyamide 12.14, polyamide 12.16, polyamide 12.18, polyamide 12.36 and polyamide 12.T blocks, mixtures thereof or copolymers thereof, preferably polyamide 11, polyamide 12, polyamide 6 or polyamide 6.10 blocks.

[0015] According to one particular embodiment, the polyether blocks are blocks of polyethylene glycol, of propylene glycol, of polytrimethylene glycol, of polytetrahydrofuran, or mixtures thereof or copolymers thereof, preferably blocks of polyethylene glycol or of polytetrahydrofuran.

[0016] According to one particular embodiment: the rigid block of the copolymer has a number average molecular weight of 400 to 20,000 g / mol, preferably 500 to 10,000 g / mol; and / or The flexible block of the copolymer has a number average molecular weight of 100 to 6000 g / mol, preferably 200 to 3000 g / mol.

[0017] According to one particular embodiment, the mass ratio of the rigid block to the flexible block of the copolymer is between 0.1 and 20, preferably between 0.3 and 3, and even more preferentially between 0.3 and 0.9.

[0018] According to one particular embodiment, the polyol has a weight-average molecular weight of less than or equal to 3000 g / mol, preferably less than or equal to 2000 g / mol and more preferentially in the range from 50 to 1000 g / mol.

[0019] According to certain embodiments, the polyol is selected from: pentaerythritol, trimethylolpropane, trimethylolethane, hexanetriol, diglycerol, methyl glucoside, tetraethanol, sorbitol, dipentaerythritol, cyclodextrin, polyether polyols containing at least three hydroxyl groups, and mixtures thereof.

[0020] The present invention also relates to foams of copolymers containing the rigid and flexible blocks described above.

[0021] According to one particular embodiment, the foam has a strength of 800 kg / m 3 Less than 600 kg / m 3 Below, more preferentially 400 kg / m 3 or less, and even more preferentially 300 kg / m 3 It has the following density:

[0022] According to one particular embodiment, the foam has a 30 minute compression set of 35% or less, preferably 30% or less.

[0023] The present invention also relates to a method for producing a method for manufacturing a semiconductor device comprising the steps of: - Mixing of the precursor of the rigid block with polyol; - Synthesis of rigid blocks; - Addition of flexible blocks; - condensation of rigid blocks and of flexible blocks, The present invention also relates to a method for producing the copolymer containing the rigid block and the flexible block, comprising:

[0024] According to a particular embodiment, the polyol is mixed in an amount ranging from 0.01% to 10% by weight, preferably from 0.01% to 5% by weight, more preferably from 0.05% to 0.5% by weight, relative to the total weight of the polyol, the precursor of the rigid block, and the flexible block.

[0025] The present invention also relates to a method for producing a method for manufacturing a semiconductor device comprising the steps of: - mixing the copolymer in the molten state with one or more additives, and a blowing agent, if desired; and - Foaming of a mixture of copolymer and blowing agent, The present invention also relates to a method for producing the foam described above, which comprises:

[0026] The present invention also relates to articles made from the foams described above.

[0027] The present invention also relates to an article comprising at least one element made of the foam described above.

[0028] According to certain embodiments, the article is selected from athletic shoe soles, large or small balls, gloves, personal protective equipment, rail tie pads, automotive parts, construction parts, and electrical and electronic equipment parts.

[0029] The present invention makes it possible to meet the needs specified above. More specifically, the present invention provides copolymers containing rigid and flexible blocks that have improved foamability and allow the formation of uniform, regular polymer foams, wherein the foams have low density and one or more advantageous properties including a high ability to recover elastic energy under low stress loads; low compression set (thus improving durability); high fatigue strength under compression; and excellent resilience. According to certain specific embodiments, the foams of the present invention are also recyclable.

[0030] This is achieved by using copolymers containing rigid and flexible blocks with specific weight average molecular weights and specific polydispersities, the copolymers being branched by specific polyol residues linking the rigid blocks of the copolymer. DETAILED DESCRIPTION OF THE INVENTION

[0031] The invention will now be described in more detail and in a non-limiting manner in the following description.

[0032] Unless otherwise indicated, all percentages are percentages by weight.

[0033] The present invention relates to rigid and flexible block copolymers, which are thermoplastic elastomer (TPE) polymers that contain rigid (or hard, rather thermoplastic behavior) and flexible (or soft, rather elastomeric behavior) blocks.

[0034] "Rigid block" is understood to mean a block having a melting point, the presence of which can be determined by differential scanning calorimetry in accordance with ISO standard 11357-3:2011 Plastics - Differential Scanning Calorimetry (DSC) Part 3.

[0035] "Soft block" is understood to mean a block having a glass transition temperature (Tg) below 0° C. The glass transition temperature can be determined by differential scanning calorimetry in accordance with ISO standard 11357-2:2011 Plastics - Differential Scanning Calorimetry (DSC) Part 2.

[0036] The rigid blocks of the copolymers according to the invention are preferably chosen from polyamide blocks, polyester blocks, polyurethane blocks and combinations thereof, such blocks being described, for example, in French patent application FR 2936803 A1.

[0037] Preferably, the rigid blocks are polyamide blocks.

[0038] Three types of polyamide blocks can be used to advantage.

[0039] According to a first type, the polyamide blocks result from the condensation of dicarboxylic acids, in particular those containing from 4 to 20 carbon atoms, preferably those containing from 6 to 18 carbon atoms, and aliphatic or aromatic diamines, in particular those containing from 2 to 20 carbon atoms, preferably those containing from 6 to 14 carbon atoms.

[0040] Examples of dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, terephthalic acid, and isophthalic acid, as well as dimerized fatty acids.

[0041] Examples of diamines include tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, 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), para-aminodicyclohexylmethane (PACM), isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN), and piperazine (Pip).

[0042] Advantageously, the polyamide blocks PA 4.12, PA 4.14, PA 4.18, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA 9.12, PA 10.10, PA 10.12, PA 10.14 and PA 10.18 are used. In the notation PA XY, as usual, 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.

[0043] According to the second type, the polyamide blocks result from the condensation of one or more α,ω-aminocarboxylic acids containing 6 to 12 carbon atoms and / or one or more lactams in the presence of dicarboxylic acids containing 4 to 12 carbon atoms or diamines. Examples of lactams include caprolactam, oenantholactam, and lauryllactam. Examples of α,ω-aminocarboxylic acids include aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

[0044] Advantageously, the second type of polyamide block is a PA 11 (polyundecaneamide), PA 12 (polydodecanamide) or PA 6 (polycaprolactam) block. In the notation PA X, X represents the number of carbon atoms originating from the amino acid residue.

[0045] 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.

[0046] In this case the polyamide PA block is: - of linear aliphatic or aromatic diamines containing X carbon atoms; - of a dicarboxylic acid containing Y carbon atoms; and - of comonomers {Z} selected from lactams and α,ω-aminocarboxylic acids containing Z carbon atoms and an equimolar mixture of at least one diamine containing X carbon atoms and at least one dicarboxylic acid containing Y carbon atoms, (X1, Y1) being different from (X, Y), Polycondensation; - said comonomer {Z} is introduced in a weight proportion advantageously ranging up to 50%, preferably up to 20% and even more advantageously up to 10%, relative to the total amount of polyamide precursor monomers; in the presence of a chain limiter selected from dicarboxylic acids, It is prepared by polycondensation of

[0047] Advantageously, a dicarboxylic acid containing Y carbon atoms is used as chain limiter, which is introduced in excess relative to the stoichiometry of the diamine.

[0048] According to one variant of this third type, the polyamide blocks are produced by condensation of at least two α,ω-aminocarboxylic acids, or at least two lactams containing 6 to 12 carbon atoms, or one lactam and one aminocarboxylic acid having no carbon atoms, optionally in the presence of a chain-limiting agent. Examples of aliphatic α,ω-aminocarboxylic acids include aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of lactams include caprolactam, oenantholactam, and lauryllactam. Examples of aliphatic diamines include hexamethylenediamine, dodecamethylenediamine, and trimethylhexamethylenediamine. Examples of alicyclic diacids 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%; are preferably hydrogenated; for example, products sold by Croda under the brand name Pripol, by BASF under the brand name Empol, or by Oleon under the brand name Radiacid, and are polyoxyalkylene α,ω-diacids. Examples of aromatic diacids include terephthalic acid (T) and isophthalic acid (I). Examples of alicyclic diamines 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-aminodicyclohexylmethane (PACM). Other commonly used diamines can be isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN) and piperazine.

[0049] Examples of polyamide blocks of the third type include: - PA 6.6 / 6, where 6.6 denotes a hexamethylenediamine unit condensed with adipic acid and 6 denotes a unit resulting from the condensation of caprolactam; - PA 6.6 / 6.10 / 11 / 12, where 6.6 denotes hexamethylenediamine condensed with adipic acid, 6.10 denotes hexamethylenediamine condensed with sebacic acid, 11 denotes units resulting from the condensation of aminoundecanoic acid, and 12 denotes units resulting from the condensation of lauryllactam.

[0050] The notation PA X / Y, PA X / Y / Z etc. refers to copolyamides where X, Y, Z etc. represent homopolyamide units as defined above.

[0051] Advantageously, the polyamide blocks of the copolymers used according to the invention are selected from the group consisting of polyamides PA 6, 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 6.9, PA 6.10, PA 6.12, PA 6.13, PA 6.14, PA 6.16, PA 6.18, PA 6.36, PA 10.4, PA 10.9, PA 10.10, PA 10.12, PA 10.13, PA 10.14, PA 10.16, PA 10.18, PA 10.36, PA 10.T, PA 12.4, PA 12.9, PA and preferably comprises a polyamide, PA 6, PA 11, PA 12, PA 6.10, PA 10.10 or PA 10.12 block, or a mixture or copolymer thereof.

[0052] The flexible blocks of the copolymers according to the invention can in particular be chosen from polyether blocks, polyester blocks, polysiloxane blocks such as polydimethylsiloxane (or PDMS) blocks, polyolefin blocks, polycarbonate blocks, and mixtures thereof.

[0053] Possible flexible blocks are described, for example, in French patent application FR 2941700 A1, page 32, line 3 to page 33, line 15, page 34, line 16 to page 37, line 13, and page 38, lines 6 to 23.

[0054] Preferably, the flexible blocks are selected from polyether blocks, polyester blocks, and combinations thereof.

[0055] Particularly advantageously, the flexible block is a polyether block.

[0056] The polyether blocks are formed from alkylene oxide units.

[0057] The polyether blocks may be, inter alia, PEG (polyethylene glycol) blocks, i.e., blocks formed from ethylene oxide units, and / or PPG (propylene glycol) blocks, i.e., blocks formed from propylene oxide units, and / or PO3G (polytrimethylene glycol) blocks, i.e., blocks formed from polytrimethylene glycol ether units, and / or PTMG (polytetramethylene glycol) blocks, i.e., blocks formed from tetramethylene glycol units, also known as polytetrahydrofuran. Copolymers may contain several types of polyethers in their chains, and copolyethers may be in block or statistical form.

[0058] It is also possible to use blocks obtained by oxyethylation of bisphenols, for example bisphenol A. The latter products are described inter alia in EP 613 919.

[0059] The polyether blocks can also be formed from ethoxylated primary amines. Examples of ethoxylated primary amines include those of the formula: TIFF2025121943000001.tif37170, where 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®.

[0060] The flexible polyether block can comprise a polyoxyalkylene block with an NH chain end, which can be obtained by cyanoacetylation of an α,ω-dihydroxylated aliphatic polyoxyalkylene block, known as a polyether diol. More specifically, the commercially available Jeffamine or Elastamine products can be used (e.g., the commercially available products Jeffamine® D400, D2000, ED 2003, and XTJ 542 from Huntsman, which are also described in JP 2004 / 346274, JP 2004 / 352794, and EP 1482011).

[0061] The polyether diol blocks are either used in unmodified form and copolycondensed with carboxyl-terminated rigid blocks, or aminated to convert them to polyether diamines and condensed with carboxyl-terminated rigid blocks.

[0062] Preferably, the copolymers according to the invention are copolymers containing polyester blocks and polyether blocks (also called COPE or copolyetherester), copolymers containing polyurethane blocks and polyether blocks (also called TPU or thermoplastic polyurethane), or copolymers containing polyamide blocks and polyether blocks (PEBA according to IUPAC, otherwise called polyether-block-amide).

[0063] While the above block copolymers comprise at least one rigid block and at least one flexible block as described above, the present invention also covers copolymers comprising three, four (or even more) different blocks selected from the blocks described in this description, provided that these blocks comprise at least a rigid block and a flexible block.

[0064] For example, the copolymers according to the invention can be segmented block copolymers (or "triblock" copolymers) comprising three different types of blocks, resulting from the condensation of several of the above blocks. The triblock can 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, for example a PEG block and a PTMG block.

[0065] Particularly advantageously, the copolymers according to the invention are copolymers containing polyamide blocks and polyether blocks (or PEBA).

[0066] PEBAs are produced from the polycondensation of reactively terminated polyamide blocks with reactively terminated polyether blocks, for example, in particular: 1) of a polyamide block having diamine chain ends with a polyoxyalkylene block having dicarboxyl chain ends; 2) of polyamide blocks with dicarboxylic chain ends with polyoxyalkylene blocks with diamine chain ends, obtained, for example, by cyanoethylation and hydrogenation of α,ω-dihydroxylated aliphatic polyoxyalkylene blocks, known as polyether diols; 3) of polyamide blocks with dicarboxylic chain ends with polyether diols, the resulting product being, in this particular case, a polyether ester amide; It is produced from polycondensation.

[0067] Polyamide blocks with dicarboxylic chain ends result, for example, from the condensation of polyamide precursors in the presence of chain-limiting dicarboxylic acids. Polyamide blocks with diamine chain ends result, for example, from the condensation of polyamide precursors in the presence of chain-limiting diamines.

[0068] Particularly preferred PEBA copolymers in the context of the present invention are copolymers comprising blocks from among the following: - PA 11 and PEG; - PA 11 and PTMG; - PA 12 and PEG; - PA 12 and PTMG; - PA 6.10 and PEG; - PA 6.10 and PTMG; - PA 6 and PEG; - PA 6 and PTMG.

[0069] The number average molecular weight of the rigid blocks in the copolymers according to the invention is preferably 400 to 20,000 g / mol, more preferentially 500 to 10,000 g / mol, and even more preferentially 600 to 6000 g / mol. In certain embodiments, the number average molecular weight of the rigid blocks in the PEBA copolymer is 400 to 500 g / mol, or 500 to 1000 g / mol, or 1000 to 1500 g / mol, or 1500 to 2000 g / mol, or 2000 to 2500 g / mol, or 2500 to 3000 g / mol, or 3000 to 3500 g / mol, or 3500 to 4000 g / mol, or 4000 to 5000 g / mol, or 5000 to 6000 g / mol, or 6000 to 7000 g / mol, or 7000 to 8000 g / mol, or 8000 g / mol. ~9000 g / mol, or 9000 to 10,000 g / mol, or 10,000 to 11,000 g / mol, or 11,000 to 12,000 g / mol, or 12,000 to 13,000 g / mol, or 13,000 to 14,000 g / mol, or 14,000 to 15,000 g / mol, or 15,000 to 16,000 g / mol, or 16,000 to 17,000 g / mol, or 17,000 to 18,000 g / mol, or 18,000 to 19,000 g / mol, or 19,000 to 20,000 g / mol.

[0070] The number average molecular weight of the flexible block is preferably 100 to 6000 g / mol, more preferentially 200 to 3000 g / mol. In certain embodiments, the number average molecular weight of the flexible block is 100 to 200 g / mol, or 200 to 500 g / mol, or 500 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 4500 g / mol, or 4500 to 5000 g / mol, or 5000 to 5500 g / mol, or 5500 to 6000 g / mol.

[0071] The number average molecular weight is determined by the chain limiter content, which can be calculated according to the following formula: M n =n モノマー ×MW 反復単位 / n 連鎖制限剤 +MW 連鎖制限剤

[0072] In the formal formula, n モノマー represents the number of moles of monomer, and n 連鎖制限剤 represents the number of moles of excess 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 molar mass of the excess diacid.

[0073] The number average molecular weights of the rigid block and of the flexible block can be measured by gel permeation chromatography (GPC) before copolymerization of both blocks.

[0074] Advantageously, the weight ratio of the rigid block to the flexible block of the copolymer is between 0.1 and 20, preferably between 0.3 and 3, and even more preferentially between 0.3 and 0.9. In particular, the weight ratio of the rigid block to the flexible block 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 between 4.5. It can be 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.

[0075] Preferably, the copolymers of the present invention have an instantaneous hardness of not more than 72 Shore D, more preferably not more than 68 Shore D. Hardness measurements can be performed according to ISO standard 868:2003.

[0076] The copolymers according to the invention are branched copolymers, which are characterized by more than two functional groups and a broad molar mass distribution.

[0077] The branched copolymer containing rigid and flexible blocks has a weight-average molecular weight Mw of more than 80,000 g / mol. Preferably, the weight-average molecular weight of the copolymer is 80,000 to 300,000 g / mol, more preferably 85,000 to 200,000 g / mol, and even more preferably 90,000 to 175,000 g / mol. The weight-average molecular weight is expressed as PMMA equivalent (used as a calibration standard) and can be measured by size exclusion chromatography in accordance with ISO standard 16014-1:2012. The copolymer is dissolved in hexafluoroisopropanol stabilized with 0.05 M potassium trifluoroacetate at a concentration of 1 g / L for 24 hours at room temperature, and then passed through a column at a flow rate of, for example, 1 ml / min, and the molar mass is measured by refractive index. Size exclusion chromatography can be performed using a column of modified silica, for example, a series of two columns and a precolumn of modified silica (e.g., a PGF column and precolumn from Polymer Standards Service), including a 1000 Å column with dimensions 300×8 mm and a particle size of 7 μm, a 100 Å column with dimensions 300×8 mm and a particle size of 7 μm, and a precolumn with dimensions 50×8 mm, at a temperature of, for example, 40° C. In certain embodiments, the branched copolymer containing rigid blocks and flexible blocks has a weight average molecular weight Mw in the range of 80,000 to 90,000 g / mol, or 90,000 to 100,000 g / mol, or 100,000 to 125,000 g / mol, or 125,000 to 150,000 g / mol, or 150,000 to 175,000 g / mol, or 175,000 to 200,000 g / mol, or 200,000 to 225,000 g / mol, or 225,000 to 250,000 g / mol, or 250,000 to 275,000 g / mol, or 275,000 to 300,000 g / mol.

[0078] The branched copolymer containing rigid and flexible blocks may have a number average molecular weight Mn ranging from 30,000 to 100,000 g / mol, preferably from 35,000 to 80,000 g / mol, and more preferably from 40,000 to 70,000 g / mol. The number average molecular weight is expressed as PMMA equivalent and can be determined according to the method described above in accordance with ISO standard 16014-1. In certain embodiments, the branched copolymer containing rigid blocks and flexible blocks has a number average molecular weight Mn in the range of 30,000 to 35,000 g / mol, or 35,000 to 40,000 g / mol, or 40,000 to 45,000 g / mol, or 45,000 to 50,000 g / mol, or 50,000 to 55,000 g / mol, or 55,000 to 60,000 g / mol, or 60,000 to 70,000 g / mol, or 70,000 to 80,000 g / mol, or 80,000 to 90,000 g / mol, or 90,000 to 100,000 g / mol.

[0079] The branched copolymer containing a rigid block and a flexible block has a z-average molar mass Mz in the range of 200,000 to 500,000 g / mol. The z-average molar mass is expressed as PMMA equivalent and can be measured according to the method described above in accordance with ISO Standard 16014-1. In certain embodiments, the branched copolymer containing a rigid block and a flexible block has a z-average molar mass Mz in the range of 200,000 to 250,000 g / mol, or 250,000 to 300,000 g / mol, or 300,000 to 350,000 g / mol, or 350,000 to 400,000 g / mol, or 400,000 to 450,000 g / mol, or 450,000 to 500,000 g / mol.

[0080] The polydispersity of a copolymer can be defined by the ratio of the weight-average molecular weight Mw of the copolymer to the number-average molecular weight Mn of the copolymer (Mw / Mn molar mass ratio) and / or by the ratio of the z-average molar mass Mz of the copolymer to the weight-average molecular weight Mw of the copolymer (Mz / Mw molar mass ratio).

[0081] The copolymers according to the present invention have a Mw / Mn molar mass ratio of 2.2 or greater, preferably 2.4 or greater. In certain embodiments, the copolymers have a Mw / Mn molar mass ratio of 2.3 or greater, or 2.4 or greater, or 2.5 or greater, or 2.6 or greater, or 2.7 or greater, or 2.8 or greater, or 2.9 or greater, or 3 or greater.

[0082] The copolymers according to the present invention may have a molar mass ratio Mw / Mn of 7 or less, preferably 6.5 or less, more preferably 6 or less.

[0083] Copolymers according to the present invention can have a Mz / Mw molar mass ratio of 1.8 or greater, preferably 2 or greater. In certain embodiments, the copolymers have a Mz / Mw molar mass ratio of 1.9 or greater, or 2 or greater, or 2.1 or greater, or 2.2 or greater, or 2.3 or greater, or 2.4 or greater, or 2.5 or greater.

[0084] The copolymers according to the invention may have a molar mass ratio Mz / Mw of 5 or less, preferably 4.5 or less, preferably 4 or less.

[0085] Copolymer synthesis The copolymers according to the invention are prepared by the addition during synthesis of one or more polyols containing at least three hydroxyl groups.

[0086] In a common and known manner, polymers containing rigid and flexible blocks can be prepared according to a two-step preparation method (comprising a first step of synthesis of the rigid block, followed by a second step of condensation of the rigid and flexible blocks) or by a one-step preparation method: a polyol is added together with the precursor of the rigid block.

[0087] A general method for the two-step preparation of PEBA copolymers having ester bonds between the PA and PE blocks (i.e., a first step of synthesizing the polyamide blocks, followed by a second step of condensing the polyamide and polyether blocks) is known and is described, for example, in document FR 2846332. A general method for the preparation of PEBA copolymers having amide bonds between the PA and PE blocks is known and is described, for example, in document EP 1482011. The polyether blocks can also be mixed with polyamide precursors and diacid chain terminators to prepare polymers containing polyamide and polyether blocks with randomly distributed units (one-step method). Regardless of the method used (two-step or one-step), a polyol is added together with the polyamide precursors.

[0088] Preferably, the copolymers according to the invention are prepared according to a two-step preparation method. Preferably, the copolymers according to the invention are prepared according to a method comprising the following steps: - Mixing of the precursor of the rigid block with polyol; - Synthesis of rigid blocks; - Addition of flexible blocks; - Condensation of rigid blocks and of flexible blocks.

[0089] The addition of polyols with functionality greater than two results in crosslinks, preferably through ester bonds, connecting the rigid blocks of the copolymer together.

[0090] Polyols containing at least three hydroxyl groups are understood to mean in particular: monomeric polyols, in particular monomeric aliphatic triols such as glycerol, trimethylolpropane, pentaerythritol, and / or - Polymeric polyols, in particular triols containing polyether chains, polycaprolactone triols, mixed polyether-polyester polyols containing at least three hydroxyl groups.

[0091] Advantageously, the polyol is chosen from: pentaerythritol, trimethylolpropane, trimethylolethane, hexanetriol, diglycerol, methyl glucoside, tetraethanol, sorbitol, dipentaerythritol, cyclodextrin, polyether polyols containing at least three hydroxyl groups, and mixtures thereof.

[0092] The weight-average molecular weight of the polyol is preferably at most 3000 g / mol, more preferentially at most 2000 g / mol; and generally ranges from 50 to 1000 g / mol, preferably from 50 to 500 g / mol, preferably from 50 to 200 g / mol.

[0093] Advantageously, the polyol is added in an amount of 0.01% to 10% by weight, preferably 0.01% to 5% by weight, more preferably 0.05% to 0.5% by weight, based on the total weight of the polyol, the precursor of the rigid block, and the flexible block. The polyol is advantageously added in an amount of 3.5 to 35 μeq / g, based on the total weight of the polyol, the precursor of the rigid block, and the flexible block.

[0094] foam The branched copolymers containing rigid and flexible blocks can be used to form foams, preferably without a crosslinking step, by mixing the copolymer in a molten state with a blowing agent, followed by a foaming step.

[0095] According to certain embodiments, the foam thus formed consists essentially of, or even consists of, the copolymer (or copolymers, if a mixture of copolymers is used) and, optionally, a blowing agent, if the blowing agent remains present in the pores of the foam, especially if the foam is a closed-pore foam.

[0096] Copolymers containing rigid and flexible blocks can be combined with various additives, such as copolymers of ethylene and vinyl acetate or EVA (e.g., those sold by Arkema under the trademark Evatane®), or copolymers of ethylene and acrylates, or copolymers of ethylene and alkyl (meth)acrylates, such as those sold by Arkema under the trademark Lotryl®. These additives make it possible to adjust the hardness of the foamed part, its appearance, and its comfort. The additives can be added to the copolymers containing rigid and flexible blocks in amounts of 0 to 50% by weight, preferably 5 to 30% by weight.

[0097] The blowing agent can be a chemical or physical agent, or can consist of any type of hollow body or any type of expandable microsphere. Preferably, the blowing agent is a physical agent, such as dinitrogen or carbon dioxide, or a hydrocarbon, chlorofluorocarbon, hydrochlorocarbon, hydrofluorocarbon, or hydrochlorofluorocarbon (saturated or unsaturated). For example, butane or pentane can be used. Also preferably, the blowing agent can be a chemical agent, such as azodicarbonamide or a mixture based on citric acid and sodium bicarbonate (NaHCO3) (such as the Hydrocerol® range of products from Clariant).

[0098] The physical blowing agent is mixed with the copolymer in liquid or supercritical form and then converted to the gas phase during the foaming process.

[0099] According to a preferred embodiment, the mixture of the copolymer and the blowing agent is poured into a mold and foamed by opening the mold. This technique allows the direct production of three-dimensional foamed articles with complex shapes.

[0100] It is also a relatively easy technique to carry out, especially compared to certain methods of melting expanded particles described in the prior art: in particular, filling a mold with expanded polymer granules and subsequently melting the particles to ensure the mechanical strength of the part without destroying the structure of the foam is a difficult operation.

[0101] Other foaming techniques that can be used are in particular "batch" foaming, extrusion foaming such as single or twin screw extrusion foaming, autoclave foaming, microwave foaming and other injection molding foaming techniques (under metering, using a breathable mold with the application of gas back pressure, or using a mold equipped with a Variotherm® system).

[0102] The foam according to the invention preferably has a strength of 800 kg / m 3 Below, more preferentially 600 kg / m 3 Below, and even more preferentially 400 kg / m 3 Particularly preferably 300 kg / m or less 3 The foam according to the present invention has a density of, for example, 25 to 800 kg / m 3 , more particularly preferably 50 to 600 kg / m 3 The density can be controlled by adapting the parameters of the manufacturing process.

[0103] Preferably, the foam has a resilience of 50% or more, preferably 55% or more, according to ISO standard 8307:2007.

[0104] Preferably, the foam has a compression set after 30 minutes according to ISO standard 7214:2012 of 35% or less, more particularly preferably 30% or less, or 25% or less.

[0105] Preferably, the foam also has good properties in terms of fatigue strength and damping.

[0106] The foams according to the invention can be used to manufacture sports equipment such as soles of sports shoes, ski shoes, midsoles, insoles or functional sole components in the form of inserts in various parts of the sole (for example heel or arch), or components of the upper in the form of reinforcements or inserts in the structure of the upper or in the form of protection.

[0107] The foams according to the invention can also be used to manufacture inflatable balls, sports gloves (eg soccer gloves), golf ball components, rackets, protective elements (jackets, helmet inner elements, covers, etc.).

[0108] The foams according to the invention have advantageous impact, vibration and noise resistance in combination with tactile properties suitable for capital goods, and can therefore also be used to manufacture railway rail tie pads or various parts in the automotive industry, in transportation, in electrical and electronic equipment, in construction or in the manufacturing industry.

[0109] According to an advantageous embodiment, foam articles according to the invention can be easily recycled, for example, by melting them in an extruder equipped with a degassing vent (after optionally chopping them into pieces). [Example]

[0110] The following examples illustrate the invention without limiting it.

[0111] Example 1 Four types of PEBA were tested.

[0112] PEBA Nos. 1, 2, and 3 are all PEBA copolymers containing a PA 11 block having a number average molecular weight of 600 g / mol and a PTMG block having a number average molecular weight of 1000 g / mol and a hardness of 32 Shore D. PEBA No. 4 is a PEBA copolymer containing a PA 11 block having a number average molecular weight of 1500 g / mol, a PTMG block having a number average molecular weight of 2000 g / mol, and a Priplast™ 1838 polyester block having a number average molecular weight of 2000 g / mol.

[0113] PEBA No. 1 is a linear PEBA. PEBA Nos. 2, 3, and 4 are branched PEBAs prepared by adding, during their synthesis, 0.1 wt. % trimethylolpropane (TMP), 0.15 wt. % trimethylolpropane, and 0.1 wt. % pentaerythritol (PET), respectively (based on the total weight of the polyol and other reactants of the copolymer).

[0114] The PEBA is prepared as directed below.

[0115] PEBA Number 1: 13 kg of 11-aminoundecanoic acid, 3.8 kg of adipic acid, and 4 kg of water are introduced (loading) into the autoclave. The reactor is closed, inertized with nitrogen, then stirred and heated under autogenous pressure to 245 ° C. The temperature is maintained for 1 hour, the pressure being 31 relative bar. The reactor is depressurized to atmospheric pressure over 1 hour. The material temperature is 240 ° C. 26.1 kg of PTMG 1000 are added, and the reactor is then placed under reduced pressure of less than 15 mbar. 86 g of Irganox 1010 are introduced, followed by 64 g of zirconium tetrabutoxide. The thickening of the reaction medium is then monitored by measuring the stirring torque. When the torque reaches a predetermined value, the reaction is stopped. The reactor is then transferred to a water tank and granulated.

[0116] PEBA Number 2: PEBA No. 2 is prepared by the same method as PEBA No. 1, except that 43 g of trimethylolpropane is also added to the loading.

[0117] PEBA 3: PEBA No. 3 is prepared by the same method as PEBA No. 1, except that 3.9 kg of adipic acid is used instead of 3.8 kg, and 64 g of trimethylolpropane is also added to the loading.

[0118] PEBA Number 4: PEBA No. 4 is prepared by the same method as PEBA No. 1, with the following exceptions: - The loading is as follows: 2 kg of adipic acid, 15.6 kg of 11-aminoundecanoic acid, 43 g of pentaerythritol, and 4 kg of water; - in a second step, load 4 kg of PTMG 2000 and 21.4 kg of Priplast™ 1838; - Finally, 86 g of Irganox 1010 and 64 g of zirconium tetrabutoxide are added.

[0119] PEBA numbers 1 and 4 correspond to counterexamples, and PEBA numbers 2 and 3 are PEBAs according to the present invention.

[0120] PEBA has the following properties: TIFF2025121943000002.tif50170

[0121] The weight-average molecular weight Mw, number-average molecular weight Mn, and z-average molar mass Mz of PEBA are expressed as PMMA equivalents and are determined by size exclusion chromatography (or gel permeation chromatography) in accordance with ISO standard 16014-1 according to the method described above.

[0122] Intrinsic viscosity is measured using an Ubbelohde tube. Measurements are carried out on 75 mg samples at a concentration of 0.5% (m / m) in m-cresol at 20°C. Intrinsic viscosity is (g / 100 g) -1and is calculated according to the following formula: Intrinsic viscosity=ln(t s / t0)×1 / C, where C=m / p×100, In the formula, t s is the flow time of the solution, t0 is the flow time of the solvent, m is the mass of the sample whose viscosity is to be determined, and p is the mass of the solvent. The present measurement corresponds to ISO standard 307, apart from the fact that the measurement temperature is 20°C instead of 25°C.

[0123] Foams are prepared from PEBA numbers 1, 2, 3 and 4.

[0124] These foams are produced using an ENGEL 160T Victory injection molding machine equipped with a Trexel Series II type physical blowing agent injection system. The operating parameters are as follows: - Barrel temperature: 190~210℃ - Holding time before mold opening: 17-28 seconds. - Cooling time: 120~180 seconds. - Mold temperature: 35~60℃. - Mold opening length: up to 12mm. - Mold: Plate mold with dimensions 2 x 100 x 100 mm.

[0125] The blowing agent used is dinitrogen, introduced at a rate of 0.7% by weight.

[0126] The various properties of the resulting foams are evaluated: - Density: according to ISO standard 845; - Δ density: characterizes the homogeneity of the foam and corresponds to the difference in density of the foam between the point closest to the injection point and the point furthest from it; the lower this quantity, the more homogeneous the foam; - Rebound resilience: according to ISO standard 8307 (a 16.8 g steel ball with a diameter of 16 mm is dropped from a height of 500 mm onto the foam sample; the rebound resilience then corresponds to the percentage of energy returned to the ball or the percentage of the initial height reached by the ball on rebound); - Compressive strain (comp. set): a measurement is carried out consisting in compressing a sample to a given degree of deformation and for a given time, then releasing the released stress and recording the residual deformation after the recovery time; the measurement is adapted from ISO standard 7214 and is measured after 30 minutes under the following conditions: 50% deformation, 22 hours holding time, 23°C temperature.

[0127] The foam properties are presented in the table below: TIFF2025121943000003.tif70170

[0128] Various densities for the same PEBA can be obtained by varying the parameters of the foam manufacturing process. The densities of Foams C and D correspond to the minimum densities achieved with PEBA Nos. 1 and 2, respectively.

[0129] The PEBA No. 2 foam (Foam D) is observed to have a lower minimum density than the foam formed from PEBA No. 1 (Foam C). Additionally, Foam D is more uniform and has a lower 30 minute compression set than Foam C, while having similar rebound resilience.

[0130] Furthermore, by comparing Foam B (made of PEBA No. 1) with Foam F (made of PEBA No. 3), it is observed that at similar densities, Foam F has a lower 30-minute compression set than Foam B.

[0131] No foam could be obtained from PEBA No. 4.

Claims

1. 1. A branched copolymer containing a rigid block and a flexible block, The branches are created by polyol residues that connect the rigid blocks of the copolymer. the polyol is a polyol containing at least three hydroxyl groups; The copolymer has a weight average molecular weight Mw of 80,000 g / mol or more, and the ratio of the weight average molecular weight Mw of the copolymer to the number average molecular weight Mn of the copolymer is 2.2 or more. Copolymer.

2. 2. Copolymer according to claim 1, having a weight-average molecular weight Mw ranging from 80,000 to 300,000 g / mol, preferably from 85,000 to 200,000 g / mol, more preferentially from 90,000 to 175,000 g / mol.

3. 3. The copolymer according to claim 1, wherein the ratio of the weight average molecular weight Mw of the copolymer to the number average molecular weight Mn of the copolymer is 2.4 or more.

4. 4. Copolymer according to any one of claims 1 to 3, wherein the ratio of the z-average molar mass Mz of the copolymer to the weight-average molecular weight Mw of the copolymer is greater than or equal to 1.8, preferably greater than or equal to 2.

5. 5. The copolymer of claim 1, wherein the rigid blocks are selected from polyamide blocks, polyester blocks, polyurethane blocks, and combinations thereof.

6. 6. The copolymer of claim 1, wherein the flexible blocks are selected from polyether blocks, polyester blocks, and combinations thereof.

7. The copolymer according to claim 1 , which is a copolymer containing polyamide blocks and polyether blocks.

8. The polyamide blocks may be of polyamide 6, polyamide 11, polyamide 12, polyamide 5.4, polyamide 5.9, polyamide 5.10, polyamide 5.12, polyamide 5.13, polyamide 5.14, polyamide 5.16, polyamide 5.18, polyamide 5.36, polyamide 6.4, polyamide 6.9, polyamide 6.10, polyamide 6. Polyamide 12, Polyamide 6.13, Polyamide 6.14, Polyamide 6.16, Polyamide 6.18, Polyamide 6.36, Polyamide 10.4, Polyamide 10.9, Polyamide 10.10, Polyamide 10.12, Polyamide 10.13, Polyamide 10.14, Polyamide 10.16, Polyamide 10.18, Polyamide 10.36, Polyamide 10.T, Polyamide 12.4, Polyamide 12.9, Polyamide 12.10, Polyamide 12.12, Polyamide 12.13, Polyamide 12.14, Polyamide 12.16, Polyamide 12.18, Polyamide 12.36, Polyamide 12.

8. The copolymer according to claim 5, which is a block of T or a mixture thereof or a copolymer thereof, preferably a block of polyamide 11, of polyamide 12, of polyamide 6 or of polyamide 6.

10.

9. 9. Copolymer according to any one of claims 6 to 8, wherein the polyether blocks are blocks of polyethylene glycol, of propylene glycol, of polytrimethylene glycol, of polytetrahydrofuran, or mixtures or copolymers thereof, preferably blocks of polyethylene glycol or of polytetrahydrofuran.

10. the rigid blocks of the copolymer have a number average molecular weight of 400 to 20,000 g / mol, preferably 500 to 10,000 g / mol, and / or the flexible block of the copolymer has a number average molecular weight of 100 to 6000 g / mol, preferably 200 to 3000 g / mol; The copolymer according to any one of claims 1 to 9.

11. Copolymer according to any one of claims 1 to 10, wherein the weight ratio of the rigid block to the flexible block of the copolymer is between 0.1 and 20, preferably between 0.3 and 3, and even more preferentially between 0.3 and 0.

9.

12. Copolymer according to any one of claims 1 to 11, in which the polyol has a weight average molecular weight of less than or equal to 3000 g / mol, preferably less than or equal to 2000 g / mol and more preferentially in the range from 50 to 1000 g / mol.

13. 13. The copolymer of any one of claims 1 to 12, wherein the polyol is selected from: pentaerythritol, trimethylolpropane, trimethylolethane, hexanetriol, diglycerol, methyl glucoside, tetraethanol, sorbitol, dipentaerythritol, cyclodextrin, polyether polyols containing at least three hydroxyl groups, and mixtures thereof.

14. A copolymer foam containing a rigid block and a flexible block according to any one of claims 1 to 13.

15. 800 kg / m ３ Preferably 600 kg / m or less ３ More preferably, 400 kg / m ３ and even more preferentially 300 kg / m ３ 15. The foam of claim 14 having a density of:

16. 16. A foam according to claim 14 or 15, having a compression set after 30 minutes of 35% or less, preferably 30% or less.

17. The following steps: - mixing the precursors of the rigid block with polyol; - synthesis of rigid blocks; - Addition of flexible blocks; - condensation of rigid blocks and of flexible blocks, 14. A method for producing a copolymer containing a rigid block and a flexible block according to claim 1, comprising:

18. 18. The method according to claim 17, wherein the polyol is mixed in an amount ranging from 0.01% to 10% by weight, preferably from 0.01% to 5% by weight, more preferably from 0.05% to 0.5% by weight, based on the total weight of the polyol, the precursor of the rigid block and the flexible block.

19. The following steps: mixing the copolymer in the melt, optionally with one or more additives and a blowing agent; and - foaming of a mixture of copolymer and blowing agent, A method for producing the foam of any one of claims 14 to 16, comprising:

20. 17. An article comprising the foam of any one of claims 14 to 16.

21. 17. An article comprising at least one element made of the foam of any one of claims 14 to 16.

22. 22. The article of claim 20 or 21, selected from the group consisting of athletic shoe soles, large or small balls, gloves, personal protective equipment, rail tie pads, automotive parts, construction parts and electrical and electronic equipment parts.

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