WO2022162048A1 - Mousse particulaire à base de tpe présentant une dureté shore a comprise entre 20d et 90d - Google Patents

Mousse particulaire à base de tpe présentant une dureté shore a comprise entre 20d et 90d Download PDF

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Publication number
WO2022162048A1
WO2022162048A1 PCT/EP2022/051856 EP2022051856W WO2022162048A1 WO 2022162048 A1 WO2022162048 A1 WO 2022162048A1 EP 2022051856 W EP2022051856 W EP 2022051856W WO 2022162048 A1 WO2022162048 A1 WO 2022162048A1
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thermoplastic
tpe
foamed
thermoplastic elastomer
composition
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PCT/EP2022/051856
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German (de)
English (en)
Inventor
Frank Prissok
Elmar Poeselt
Peter Gutmann
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Basf Se
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Publication of WO2022162048A1 publication Critical patent/WO2022162048A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/26—Elastomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/26—Elastomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a foamed granulate consisting of a composition (Z1), wherein the composition contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2);
  • TPE-1 thermoplastic elastomer
  • TPE-2 thermoplastic elastomer
  • Foams in particular also particle foams, have been known for a long time and are widely described in the literature, e.g. in Ullmann's "Encyclopedia of Industrial Chemistry", 4th edition, volume 20, page 416 ff.
  • Highly elastic, predominantly closed-cell foams such as particle foams made from thermoplastic polyurethane, which are produced in autoclaves or using the extruder process, have good mechanical properties and, in some cases, good resilience as well.
  • Hybrid foams made from particles of thermoplastic elastomers and system foam or binders are also known.
  • the properties of the foam can also be influenced by post-treatment of the foam, such as tempering.
  • TPU foams or foam particles or else foamed granules based on thermoplastic polyurethane are disclosed in WO 94/20568 A1.
  • a disadvantage of the TPU foams described in WO 94/20568 A1 is the high energy consumption during production and processing. A water vapor pressure of 4.5 bar to 7 bar at temperatures of 145°C to 165°C is used.
  • WO 94/20568 A1 describes expanded, i.e. foamed, TPU particles which can be processed into molded parts. These TPU foam particles are produced at temperatures of 150° C. and higher and, according to the examples, have a bulk density of between 55 and 180 g/l, which is a disadvantage when these particles are transported and stored because of the increased space requirement.
  • JP2019157107 and CN 110294860 describe a composition comprising a thermoplastic polyamide elastomer and a thermoplastic polyurethane elastomer and the use of such compositions for the production of shoe soles.
  • CN110355970 describes a manufacturing process for colored TPU foam particles and moldings made from them.
  • CN 109867946 and CN 107151373 disclose thermoplastic polyurethane foam particles, a further polymer being used in addition to a thermoplastic polyurethane elastomer.
  • JP2016190989 discloses particle foams based on polyamides.
  • WO 2018/232968 A1 describes processes for producing foams based on thermoplastic polyester elastomers
  • CN 108239386 discloses an extruded and foamed thermoplastic polyurethane elastomer particle and a manufacturing method thereof.
  • CN 105968767 describes a polymethylethylene carbonate foam material and manufacturing processes thereof.
  • WO 2007/082838 A1 discloses an expandable, preferably particulate, thermoplastic polyurethane containing blowing agent, the thermoplastic polyurethane having a Shore hardness of between A 44 and A 84. The Shore hardness of the TPU is measured on the compact, i.e. non-expanded TPU.
  • WO 2007/082838 A1 also discloses processes for producing expandable, preferably particulate, thermoplastic polyurethane containing blowing agent and processes for producing expanded thermoplastic polyurethane and processes for producing foam based on thermoplastic polyurethane and foams or expanded thermoplastic polyurethanes obtainable in this way.
  • the mechanical properties, in particular the elongation at break, of the moldings obtainable from the foamed granules are not sufficient for many applications.
  • the rebound resilience of the foams known in the prior art is not sufficient for many applications.
  • One of the objects on which the present invention is based was therefore to find foamed granules or moldings produced from foamed granules with very high rebound in combination with good mechanical properties.
  • this object is achieved by a foamed granulate consisting of a composition (Z1), wherein the composition contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2 ).
  • TPE-1 thermoplastic elastomer
  • TPE-2 thermoplastic elastomer
  • Blends can also be used to combine and set different glass temperatures in one material.
  • the foamed granules according to the invention consist of the composition (Z1).
  • the composition (Z1) contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2).
  • the composition (Z1) can also contain other components, in particular other thermoplastic elastomers.
  • the thermoplastic elastomer (TPE-1) has a Shore D hardness in the range from 20 to 90.
  • the properties of the thermoplastic elastomer (TPE-2) can vary widely.
  • thermoplastic elastomers are known per se to those skilled in the art.
  • the thermoplastic elastomer (TPE-1) can be a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester or a thermoplastic styrene-butadiene block copolymer, provided it has a Shore D hardness in the range from 20 to 90.
  • thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters or thermoplastic styrene-butadiene block copolymers.
  • thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides or thermoplastic copolyester elastomers.
  • thermoplastic polyether esters and polyester esters can be prepared by all standard processes known from the literature by transesterification or esterification of aromatic and aliphatic dicarboxylic acids having 4 to 20 carbon atoms or their esters with suitable aliphatic and aromatic diols and polyols (cf. “Polymer Chemistry ", Interscience Publ., New York, 1961, pp. 111-127; Kunststoff Handbuch, Volume VIII, C. Hanser Verlag, Kunststoff 1973 and Journal of Polymer Science, Part A1, 4, pages 1851-1859 (1966)).
  • Suitable aromatic dicarboxylic acids include, for example, phthalic acid, iso- and terephthalic acid and their esters.
  • Suitable aliphatic dicarboxylic acids include, for example, cyclohexane-1,4-dicarboxylic acid, adipic acid, sebaconic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids, and maleic acid, fumaric acid, aconitic acid, itoconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated dicarboxylic acids.
  • Polyether oils of the general formula HO-(CH2)n-O-(CH2)m-OH, where n is the same or different from m and n or m 2 to 20, unsaturated diols and polyether oils such as, for example, butene-1,4-diol; diols and polyethers containing aromatic units; as well as polyester.
  • thermoplastic elastomers with a block copolymer structure used according to the invention preferably contain vinylaromatic, butadiene and isoprene and also polyolefin and vinylic units, for example ethylene, propylene and vinyl acetate units. Styrene-butadiene copolymers are preferred.
  • thermoplastic elastomers used according to the invention with a block copolymer structure are preferably chosen so that their melting points are ⁇ 300°C, preferably ⁇ 250°C, in particular ⁇ 220°C.
  • thermoplastic elastomers used according to the invention with a block copolymer structure polyetheramides, polyetheresters and polyesteresters are preferably selected such that their melting points are >95°C, preferably >110°C, in particular >140°C.
  • thermoplastic elastomers used according to the invention with a block copolymer structure polyetheramides, polyetheresters and polyesteresters can be partially crystalline or amorphous.
  • thermoplastic elastomer (TPE-1) contained in the composition (Z1) is particularly advantageous, a thermoplastic polyurethane with a Shore D hardness in the range from 20 to 90.
  • the present invention also relates to a foamed granulate as described above, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane.
  • TPE-1 thermoplastic elastomer
  • thermoplastic elastomer (TPE-2) can also be a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester or a thermoplastic styrene-butadiene block copolymer. Accordingly, the present invention also relates to a further embodiment of a foamed granulate as described above, wherein the thermoplastic elastomer (TPE-2) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyether esters, polyester esters or thermoplastic styrene butadiene block copolymers.
  • the foamed granules consisting of the composition (Z1) have particularly advantageous property profiles when the thermoplastic elastomer (TPE-2) has a particularly low hard segment content, for example a hard segment content of less than 25%.
  • the hard segment content or hard segment proportion is determined according to the formula disclosed in WO 2007/118827 A1.
  • the present invention also relates to a further embodiment of a foamed granulate as described above, wherein the thermoplastic elastomer (TPE-2) has a hard segment content of less than 25%, for example less than 23% or less than 20%.
  • the composition (Z1) contains at least the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2).
  • the composition can also contain other components.
  • the composition (Z1) preferably contains no further elastomers in addition to the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2).
  • the ratio of the thermoplastic elastomers used (TPE-1) and (TPE-2) can vary within wide ranges.
  • the composition (Z1) preferably contains the thermoplastic elastomer (TPE-2) in an amount in the range from 1 to 60% by weight, based on the total composition (Z1), more preferably in an amount in the range from 5 to 50% by weight. %, particularly preferably in an amount in the range from 10 to 30% by weight, based in each case on the total composition (Z1).
  • thermoplastic elastomer (TPE-1) can be a thermoplastic polyetheramide and the thermoplastic elastomer (TPE-2) can be a thermoplastic polyurethane or the thermoplastic elastomer (TPE-1) can be a thermoplastic polyetherester and the thermoplastic elastomer ( TPE-2) a thermoplastic polyurethane or the thermoplastic elastomer (TPE-1) can be a thermoplastic polyurethane and the thermoplastic elastomer (TPE-2) can be a thermoplastic polyurethane or the thermoplastic elastomer (TPE-1) can be a thermoplastic styrene-butadiene block copolymer and the thermoplastic elastomer (TPE-2) can be a thermoplastic polyurethane or the thermoplastic elastomer (TPE-1) can be a thermoplastic polyurethane and the thermoplastic elastomer (TPE-2) can be a thermoplastic polyurethane or the thermoplastic elast
  • thermoplastic polyurethane is preferably used as the thermoplastic elastomer (TPE-1) and (TPE-2).
  • the composition (Z1) accordingly preferably contains a first thermoplastic elastomer (TPE-1) and a second thermoplastic elastomer (TPE-2), both the (TPE-1) being a thermoplastic polyurethane (TPU-1) and also the ( TPE-2) is a thermoplastic polyurethane (TPU-2).
  • Thermoplastic polyurethanes are known from the prior art. They are usually obtained by reacting a polyisocyanate composition with a polyol composition, the polyol composition usually comprising a polyol and a chain extender.
  • thermoplastic polyurethanes which are obtained or obtainable by reacting a polyisocyanate composition with a polyol composition.
  • the polyol composition usually contains at least one polyol.
  • Polyols are known in principle to those skilled in the art and are described, for example, in "Plastics Manual, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. Polyester oils or polyether oils are particularly preferably used as polyols.
  • polycarbonates can be used. Copolymers can also be used within the scope of the present invention.
  • the number-average molecular weight of the polyols used according to the invention is preferably between 0.5 ⁇ 10 3 g/mol and 8 ⁇ 10 3 g/mol, preferably between 0.6 ⁇ 10 3 g/mol and 5 ⁇ 10 3 g/mol, in particular between 0.8 ⁇ 10 3 g/mol and 3 x 10 3 g/mol.
  • polyether oils are suitable, but also polyester oils, block copolymers and hybrid polyols such as poly(ester/amide).
  • preferred polyether oils are polyethylene glycols, polypropylene glycols, polyadipates, polycarbonate(diol)s and polycaprolactone.
  • the polyol composition preferably contains a polyol selected from the group consisting of polyether oils, polyester oils, polycaprolactones and polycarbonates.
  • Suitable block copolymers are, for example, those which have ether and ester blocks, such as polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or polyethers with polycaprolactone end blocks.
  • preferred polyether oils are polyethylene glycols and polypropylene glycols.
  • Polycaprolactone is also preferred.
  • the polyol used advantageously has a molecular weight Mn in the range from 500 g/mol to 4000 g/mol, preferably in the range from 800 g/mol to 3000 g/mol.
  • the polyols used or the polyol composition preferably have an average functionality of between 1.8 and 2.3, preferably between 1.9 and 2.2, in particular 2.
  • the polyols used according to the invention preferably have only primary hydroxyl groups.
  • At least one polyol composition containing at least polytetrahydrofuran is preferably used.
  • the polyol composition can also contain other polyols in addition to polytetrahydrofuran.
  • polyethers are suitable as further polyols, but also polyesters, block copolymers and hybrid polyols such as poly(ester/amide).
  • Suitable block copolymers are, for example, those which have ether and ester blocks, such as polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or polyethers with polycaprolactone end blocks.
  • preferred polyether oils are polyethylene glycols and polypropylene glycols. Another preferred polyol is polycaprolactone.
  • suitable polyols are polyether oils such as polytrimethylene oxide or polytetramethylene oxide.
  • the polyol composition contains at least one polytetrahydrofuran and at least one other polyol selected from the group consisting of another polytetramethylene oxide (PTHF), polyethylene glycol, polypropylene glycol and polycaprolactone.
  • PTHF polytetramethylene oxide
  • the polytetrahydrofuran preferably has a number-average molecular weight Mn in the range from 500 g/mol to 5000 g/mol, more preferably in the range from 550 to 2500 g/mol, particularly preferably in the range from 650 to 2000 g/mol.
  • the composition of the polyol composition can vary within wide limits.
  • the content of the first polyol, preferably polytetrahydrofuran can be in the range from 15% to 85%, preferably in the range from 20% to 80%, more preferably in the range from 25% to 75%.
  • the polyol composition can also contain a solvent. Suitable solvents are known per se to those skilled in the art.
  • the number-average molecular weight Mn of the polytetrahydrofuran is, for example, in the range from 500 g/mol to 5000 g/mol, preferably in the range from 500 to 3000 g/mol. More preferably, the number-average molecular weight Mn of the polytetrahydrofuran is in the range from 500 to 1400 g/mol.
  • mixtures of different polytetrahydrofurans can also be used, i.e. mixtures of polytetrahydrofurans with different molecular weights.
  • Suitable chain extenders are, for example, compounds which have at least two functional groups which are reactive toward isocyanates, for example hydroxyl groups, amino groups or thiol groups.
  • Suitable chain extenders are compounds selected from the group consisting of aliphatic and aromatic diols with a molecular weight of ⁇ 500 g/mol, preferably ⁇ 350 g/mol.
  • diols are preferably used as chain extenders.
  • Aliphatic, araliphatic, aromatic and/or cycloaliphatic diols with a molecular weight of 50 g/mol to 220 g/mol can preferably be used here.
  • Alkanediols having 2 to 10 carbon atoms in the alkylene radical are preferred, in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and/or deca-alkylene glycols.
  • 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol particular preference is given to 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol.
  • branched compounds such as 1,4-cyclohexyldimethanol, 2-butyl-2-ethylpopanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, pinacol, 2-ethyl-1,3-hexanediol, 1,4- Cyclohexanediol or N-phenyldiethanolamine are suitable as chain extenders in the context of the present invention.
  • Mixed compounds such as 4-aminobutanol are also suitable.
  • chain extenders can also be used.
  • compounds with amino groups can also be used, for example diamines. Mixtures of diols and diamines can also be used.
  • the amount of chain extender used and of the polyols used can vary within wide ranges.
  • the chain extender mixture is chosen such that the softer of the thermoplastic elastomers used, for example the TPU, has a softening point of less than 190° C., preferably less than 160° C. and very preferably less than 150° C.
  • the softening point is, in the context of the present invention, using DMA (measured on a 2 mm injection molded sheet tempered for 20 h at 100° C. based on DIN EN ISO 6721-1:2011, with a frequency of 1 Hz and a Heating rate of 20 K/min measured from - 80 °C to 200 °C.
  • DMA measured on a 2 mm injection molded sheet tempered for 20 h at 100° C. based on DIN EN ISO 6721-1:2011, with a frequency of 1 Hz and a Heating rate of 20 K/min measured from - 80 °C to 200 °C.
  • a polyisocyanate composition containing at least one polyisocyanate is used to produce the thermoplastic polyurethane.
  • preferred polyisocyanates are diisocyanates, in particular aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates.
  • Suitable isocyanates are known per se to those skilled in the art.
  • the isocyanate composition it is also possible for the isocyanate composition to contain 4,4'-methylenediphenyl diisocyanate and at least one further methylenediphenyl diisocyanate.
  • methylenediphenyl diisocyanate is understood as meaning 2,2'-, 2,4'- and/or 4,4'-diphenylmethane diisocyanate or a mixture of two or three isomers.
  • 2,2'- or 2,4'-diphenylmethane diisocyanate or a mixture of two or three isomers can be used as a further isocyanate.
  • the polyisocyanate composition can also contain other polyisocyanates.
  • pre-reacted products can be used as isocyanate components in which part of the OH components in an upstream reaction step with a Isocyanate are reacted.
  • the actual polymer reaction the products obtained are reacted with the remaining OH components and then form the thermoplastic polyurethane.
  • Customary aliphatic and/or cycloaliphatic diisocyanates are used as aliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 2-ethyltetramethylene-1,4 - diisocyanate, hexamethylene-1,6-diisocyanate (HDI), pentamethylene-1,5-diisocyanate, butylene-1,4-diisocyanate, trimethylhexamethylene-1,6-diisocyanate, 1-isocyanato-3,3,5-trimethyl- 5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and/or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cycl
  • Preferred aliphatic polyisocyanates are hexamethylene-1,6-diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and 4,4'-, 2,4'- and/or 2,2- '- methylenedicyclohexyl diisocyanate (H12MDI); 4,4'-, 2,4'- and/or 2,2'-methylenedicyclohexyl diisocyanate (H12MDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane or mixtures thereof are particularly preferred.
  • HDI hexamethylene-1,6-diisocyanate
  • H12MDI 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and 4,4'-, 2,4'- and/or 2,2- '- methylenedicyclohexyl diisocyan
  • Suitable aromatic diisocyanates are, in particular, 1,5-naphthylene diisocyanate (NDI), 2,4- and/or 2,6-tolylene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanato-diphenyl (TODI), p-Phenylene diisocyanate (PDI), diphenylethane-4,4'-diisocyanate (EDI), diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and/or phenylene diisocyanate.
  • NDI 1,5-naphthylene diisocyanate
  • TDI 2,4- and/or 2,6-tolylene diisocyanate
  • TODI 3,3'-dimethyl-4,4'-diisocyanato-diphenyl
  • PDI p-Phen
  • polyisocyanate compositions containing 4,4'-MDI and 2,4-MDI polyisocyanate compositions containing 4,4'-MDI and 3,3'-dimethyl-4,4'-diisocyanato-diphenyl ( TODI) or polyisocyanate compositions containing 4,4'-MDI and 1,5-naphthylene diisocyanate (NDI).
  • TODI polyisocyanate compositions containing 4,4'-MDI and 2,4-MDI
  • NDI 1,5-naphthylene diisocyanate
  • the polyisocyanate composition usually contains 4,4'-MDI in an amount of 2 to 50%, based on the total polyisocyanate composition, and the further isocyanate in an amount of 3 to 20%, based on the total polyisocyanate composition.
  • Preferred examples of higher functional isocyanates are triisocyanates, e.g. B. triphenylmethane-4,4',4"-triisocyanate, furthermore the cyanurates of the aforementioned diisocyanates, as well as the oligomers obtainable by partial reaction of diisocyanates with water, e.g of semi-blocked diisocyanates with polyols having on average more than two and preferably three or more hydroxy groups.
  • the polyisocyanate composition can also contain one or more solvents. Suitable solvents are known to those skilled in the art. For example, non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons are suitable.
  • Crosslinking agents can also be used within the scope of the present invention, for example the abovementioned higher-functionality polyisocyanates or polyols or else other higher-functionality molecules having a plurality of functional groups which are reactive toward isocyanates. It is also possible within the scope of the present invention to achieve crosslinking of the products by using an excess of isocyanate groups in relation to the hydroxyl groups.
  • the components are used in a ratio such that the molar ratio of the sum of the functionalities of the polyol composition used to the sum of the functionalities of the isocyanate composition used is in the range from 1:0.8 to 1:1.3.
  • the ratio is preferably in the range from 1:0.9 to 1:1.2, more preferably in the range from 1:0.965 to 1:1.11, more preferably in the range from 1:0.97 to 1:1.11 , more preferably in the range from 1:0.97 to 1:1.05, particularly preferably in the range from 1:0.98 to 1:1.03.
  • the index is defined here by the ratio of the total isocyanate groups used in the reaction to the isocyanate-reactive groups, ie in particular the reactive groups of the polyol component. If the index is 1000, there is one active hydrogen atom for one isocyanate group. At indexes above 1000, there are more isocyanate groups than isocyanate-reactive groups.
  • the index in the reaction of the components is preferably in the range from 965 to 1110, for example in the range from 970 to 1110, more preferably in the range from 970 to 1050, particularly preferably in the range from 980 to 1030.
  • additives can be added during the production of the thermoplastic polyurethane, for example catalysts or auxiliaries and additives.
  • Additives and auxiliaries are known per se to those skilled in the art. According to the invention, combinations of several additives can also be used. Suitable auxiliaries and additives can be found, for example, in the Plastics Handbook, Volume VII, published by Vieweg and Höchtlen, Carl Hanser Verlag, Kunststoff 1966 (S103-113).
  • Suitable catalysts are also known in principle from the prior art.
  • Suitable catalysts are, for example, organic metal compounds selected from the group consisting of tin, titanium, zirconium, hafnium, bismuth, zinc, aluminum and iron organyls, such as tin organyl compounds, preferably tin dialkyls such as dimethyltin or diethyltin, or organotin compounds of aliphatic carboxylic acids, preferably tin diacetate, tin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth compounds such as bismuth alkyl compounds or the like, or iron compounds, preferably iron(MI) acetylacetonate or the metal salts of carboxylic acids such as tin(II) isooctoate, tin dioctoate , titanic acid ester or bismuth (III) neodecanoate.
  • organyls such as
  • the proportion of hard segments in the thermoplastic polyurethanes (TPU-1) used according to the invention is usually in the range from 5 to 70%, in particular in the range from 10 to 50%, preferably in the range from 15 to 45%.
  • the hard segment content or hard segment proportion is determined according to the formula disclosed in WO 2007/118827 A1.
  • composition (Z1) is well suited for the production of foamed materials.
  • the composition (Z1) can be processed in a manner known per se to give foamed materials.
  • additives such as blowing agents, cell regulators, surface-active substances, nucleating agents, fillers, hollow microspheres and/or release agents are used. Suitable processes and additives are disclosed, for example, in WO2014/198779 A1, in WO 2007/082838 A1 or WO 94/20568 A1.
  • the composition (Z1) is produced in a manner known per se from the individual thermoplastic elastomers (TPE-1) and (TPE-2) and optionally further components. Suitable methods are, for example, customary mixing methods in a kneader or an extruder.
  • the present invention also relates to a method for producing a foamed granulate.
  • the present invention also relates to a method for producing a foamed granulate comprising the steps
  • composition (i) providing a composition (Z1) in the form of granules, the composition containing at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2);
  • step (ii) producing a foamed granulate from the granulate provided according to step (i).
  • Suitable processes for producing a foamed granulate according to step (ii) from the granulate provided according to step (i) are, for example, the suspension process or the extrusion process.
  • the present invention relates to a method for producing a foamed granulate comprising the steps (i) providing a composition (Z1), wherein the composition contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2);
  • composition (Z1) can be used in the form of a melt or in the form of granules.
  • the method according to the invention can include further steps, for example temperature adjustments.
  • the non-expanded polymer mixture of the composition (Z1) required for the production of the foamed granules is produced in a known manner from the individual components and optionally further components such as, for example, processing aids, stabilizers, compatibilizers or pigments.
  • Suitable methods are, for example, conventional mixing methods using a kneader, continuously or batchwise, or an extruder such as a co-rotating twin-screw extruder.
  • compatibilizers or auxiliaries such as stabilizers
  • auxiliaries such as stabilizers
  • these can also be incorporated into the components during their manufacture.
  • the individual components are usually combined before the mixing process or metered into the apparatus that takes over the mixing.
  • the components are all metered into the intake and conveyed together into the extruder, or individual components are added via a side metering.
  • Processing takes place at a temperature at which the components are in a plasticized state.
  • the temperature depends on the softening or melting ranges of the components, but must be below the decomposition temperature of each component.
  • Additives such as pigments or fillers or other of the usual auxiliaries mentioned above are not melted, but incorporated in the solid state.
  • the foamed granules or particle foams according to the invention generally have a bulk density of 50 g/l to 200 g/l, preferably 60 g/l to 180 g/l, particularly preferably 80 g/l to 150 g/l.
  • the bulk density is measured analogously to DIN ISO 697:1984, in which, in contrast to the standard, a vessel with a volume of 10 l is used instead of a vessel with a volume of 0.5 l when determining the above values, since especially with the foam particles with low density and large mass, a measurement with a volume of only 0.5 l is too imprecise.
  • the diameter of the individual particles of the foamed granules is between 0.5 and 30; preferably 1 to 15 and in particular between 3 to 12 mm.
  • diameter means the longest dimension.
  • the composition (Z) comprises the composition (Z1).
  • the composition (Z) can contain further components.
  • the composition (Z) preferably consists of the composition (Z1).
  • the amount of blowing agent is preferably from 0.1 to 40, in particular from 0.5 to 35 and particularly preferably from 1 to 30 parts by weight, based on 100 parts by weight of the amount of composition (Z) used.
  • composition (Z) according to the invention in the form of granules
  • composition (Z) according to the invention in the form of granules
  • the unexpanded granules preferably have an average minimum diameter of 0.2-10 mm (determined via 3D evaluation of the granules, eg via dynamic image analysis using an optical measuring apparatus called PartAn 3D from Microtrac).
  • the individual granules generally have an average mass in the range from 0.1 to 50 mg, preferably in the range from 4 to 40 mg and particularly preferably in the range from 7 to 32 mg. This mean mass of the granules (particle weight) is determined as the arithmetic mean by weighing 10 granulate particles each time 3 times.
  • One embodiment of the above method comprises impregnating the granules with a blowing agent under pressure and then expanding the granules in steps (I) and (II):
  • step (I) can be carried out in the presence of water and optionally suspension auxiliaries or only in the presence of the blowing agent and the absence of water.
  • Suitable suspension aids are, for example, water-insoluble inorganic stabilizers such as tricalcium phosphate, magnesium pyrophosphate, metal carbonates; also polyvinyl alcohol and surfactants such as sodium dodecylarylsulfonate. They are usually used in amounts of 0.05 to 10% by weight, based on the composition according to the invention.
  • the impregnation temperatures are in the range of 100°C-200°C, the pressure in the reaction vessel being between 2-150 bar, preferably between 5 and 100 bar, particularly preferably between 20 and 60 bar, the impregnation time is generally 0.3 to 10 hours.
  • Suitable blowing agents for carrying out the process in a suitable closed reaction vessel are, for example, organic liquids and gases which are in a gaseous state under the processing conditions, such as hydrocarbons or inorganic gases or mixtures of organic liquids or gases and inorganic gases, these also being combined can become.
  • suitable hydrocarbons are halogenated or non-halogenated, saturated or unsaturated aliphatic hydrocarbons, preferably non-halogenated, saturated or unsaturated aliphatic hydrocarbons.
  • Preferred organic blowing agents are saturated, aliphatic hydrocarbons, especially those having 3 to 8 carbon atoms, such as butane or pentane.
  • Suitable inorganic gases are nitrogen, air, ammonia or carbon dioxide, preferably nitrogen or carbon dioxide or mixtures of the gases mentioned above.
  • the impregnation of the granules with a blowing agent under pressure comprises processes and subsequent expansion of the granules in steps (a) and (ß):
  • Suitable blowing agents in this variant of the process are volatile organic compounds with a boiling point of -25°C to 150°C, in particular -10°C to 125°C, at standard pressure 1013 mbar.
  • Hydrocarbons preferably halogen-free
  • C4-10 alkanes for example the isomers of butane, pentane, hexane, heptane and octane, particularly preferably isopentane.
  • Other possible blowing agents are sterically demanding compounds such as alcohols, ketones, esters, ethers and organic carbonates. Carbon dioxide or nitrogen or mixtures of carbon dioxide and nitrogen are also suitable as blowing agents in the context of the present invention.
  • the composition in step (ii) is mixed under pressure in an extruder, with melting, with the blowing agent which is fed to the extruder.
  • the mixture containing blowing agent is pressed out under pressure, preferably with moderately controlled counter pressure (e.g. underwater granulation) and granulated.
  • moderately controlled counter pressure e.g. underwater granulation
  • the strand of melt foams and the particle foams are obtained by granulation.
  • Suitable extruders are all the usual screw machines, in particular single-screw and twin-screw extruders (eg type ZSK from Werner & Pfleiderer), co-kneaders, Kombiplast machines, M PC kneading mixers, FCM mixers, KEX kneading screw extruders and shear roller extruders, such as they eg in Saechtling (ed.), Kunststoff-Taschenbuch, 27th edition, Hanser-Verlag Kunststoff 1998, chap. 3.2.1 and 3.2.4.
  • the extruder is usually operated at a temperature at which the composition (Z1) is in the form of a melt, for example at 120° C.
  • the components can be melted and blended in a first extruder and a blowing agent can be injected.
  • the impregnated melt is homogenized and the temperature and/or pressure is adjusted. If, for example, three extruders are combined, the mixing of the components and the injection of the blowing agent can also be divided into two different parts of the process. If, as is preferred, only one extruder is used, then all the process steps, melting, mixing, injection of the blowing agent, homogenization and setting the temperature and/or the pressure are carried out in one extruder.
  • the corresponding foamed granules which may even have already been colored, can be produced directly from the granules by impregnating the corresponding granules with a supercritical fluid from which the supercritical fluid is produced removed is followed by
  • Suitable supercritical fluids are, for example, those described in WO2014150122 or , for example carbon dioxide, nitrogen dioxide, ethane, ethylene, oxygen or nitrogen, preferably carbon dioxide or nitrogen.
  • the supercritical fluid can also contain a polar liquid with a Hildebrand solubility parameter equal to or greater than 9 MPa 1/2 .
  • the supercritical fluid or the heated fluid may also contain a colorant, thereby obtaining a colored foamed article.
  • the particles can be provided with an antiblocking agent before and/or after foaming.
  • Suitable antiblocking agents are, for example, talc, metal compounds such as tricalcium phosphate, calcium carbonate, silicic acids, in particular pyrogenic silicic acids such as Aerosil(R) from Degussa, salts of long-chain (eg C 10-22) carboxylic acids, for example stearic acid salts such as calcium stearate, esters of long-chain carboxylic acids, for example glycerol esters such as the glycerol stearates, and silicone oils.
  • the antiblocking agent is generally applied to the particles by mixing, spraying, tumbling or other customary methods.
  • the amount of blowing agent, impregnation time, cooling time, cooling rate, type and amount of additives, type of blowing agent, foaming process, or process parameters such as residence time, temperature or shear can be varied in order to influence the properties of the foam particles obtained.
  • the present invention also relates to a foamed granulate as described above, the closed-cell content of the foam being greater than 60%, determined according to DIN ISO 4590:2016.
  • the expanded particles are generally at least approximately spherical and usually have an average diameter at the narrowest point of 1 mm to 20 mm, preferably 2 mm to 12 mm and in particular 3 mm to 10 mm.
  • the present invention also relates to a foamed granulate, as described above, wherein the particles have an average diameter in the range of 1 mm to 20 mm, determined at the narrowest point, measured using a scale microscope.
  • Another object of the present invention is a shaped body produced from the foamed granules according to the invention.
  • the corresponding moldings can be produced by methods known to those skilled in the art.
  • Shaped bodies can be produced from the foamed granules according to the invention, for example by welding them together in a closed mold under the action of heat.
  • the particles are filled into the mold and, after the mold is closed, steam or hot air is introduced, as a result of which the particles expand further and fuse together to form a foam, preferably with a density in the range from 8 to 600 g/l.
  • the foams can be semi-finished products, for example panels, profiles or webs, or finished molded parts with a simple or complicated geometry. Accordingly, the term includes foam, foam semi-finished products and foam moldings.
  • the present invention also relates to a method for producing a shaped body, comprising the steps
  • thermoplastic elastomer TPE-1
  • Shore D hardness in the range from 20 to 90
  • thermoplastic elastomer-2 TPE-2
  • step (b) Production of a shaped body from the foamed granulate provided according to step (a).
  • the molding can be produced from the foamed granules according to the invention in a manner known per se.
  • a suitable method is, for example, welding using steam, hot air or high-energy radiation.
  • a preferred method for producing a foam molding comprises the following steps:
  • step (B) Fusion of the foamed granules according to the invention from step (i).
  • the fusing in step (B) preferably takes place in a closed form, it being possible for the fusing to take place using steam, hot air (as described, for example, in EP1979401 B1) or energetic radiation (microwaves or radio waves).
  • the present invention also relates to a method for producing a shaped body as described above, wherein the shaped body is produced in step (b) by welding the particles provided in step (a) using steam, hot air or high-energy radiation.
  • the temperature when fusing the foamed granules is preferably below or close to the melting point of the polymer from which the foamed granules were produced. Accordingly, for common polymers, the temperature for fusing the foamed granules is between 100.degree. C. and 180.degree. C., preferably between 120 and 150.degree.
  • Temperature profiles / residence times can be determined individually, e.g. in analogy to the methods described in US20150337102 or EP2872309B1.
  • Welding using energetic radiation generally takes place in the frequency range of microwaves or radio waves, if necessary in the presence of water or other polar liquids, such as, for example, microwave-absorbing hydrocarbons containing polar groups (such as, for example, esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols) and can be carried out analogously to the methods described in EP3053732A or WO1 6146537.
  • polar liquids such as, for example, microwave-absorbing hydrocarbons containing polar groups (such as, for example, esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols) and can be carried out analogously to the methods described in EP3053732A or WO1 6146537.
  • the foamed granules can also contain coloring agents.
  • the addition of dyes can be done in different ways.
  • the foamed granules produced can be colored after production.
  • the corresponding foamed granules are brought into contact with a carrier liquid containing a dye, the carrier liquid (TF) having a polarity which is suitable for sorption of the carrier liquid into the foamed granules.
  • a carrier liquid containing a dye the carrier liquid (TF) having a polarity which is suitable for sorption of the carrier liquid into the foamed granules.
  • TF carrier liquid
  • Suitable dyes are, for example, inorganic or organic pigments. Examples of suitable natural or synthetic inorganic pigments are carbon black, graphite, titanium oxides, iron oxides, zirconium oxides, cobalt oxide compounds, chromium oxide compounds, copper oxide compounds.
  • Suitable organic pigments are, for example, azo pigments and polycyclic pigments.
  • the color can be added during the production of the foamed granules.
  • the colorant can be added during manufacture of the foamed granules via extrusion into the extruder.
  • the supercritical fluid or the heated fluid can contain a dye.
  • the moldings according to the invention have advantageous properties for the above-mentioned applications in the shoe or sports shoe sector.
  • the tensile and compression properties of the moldings produced from the foamed granules are characterized in that the tensile strength is above 600 kPa (DIN EN ISO 1798, April 2008) and the elongation at break is above 100% (DIN EN ISO 1798, April 2008) .
  • the rebound resilience of the moldings made from the foamed granules is above 55% (analogous to DIN 53512, April 2000; the deviation from the standard is the test body height, which should be 12 mm, but this test is carried out with 20 mm to avoid "punching through”. of the sample and to avoid measuring the background).
  • the density of the moldings produced is advantageously between 75 and 375 kg/m 3 , preferably between 100 and 300 kg/m 3 , particularly preferably between 150 and 200 kg/m 3 (DIN EN ISO 845, October 2009).
  • the ratio of the density of the molding to the bulk density of the foamed granules according to the invention is generally between 1.5 and 2.5, preferably 1.8 to 2.0.
  • the subject matter of the invention is also the use of a foamed granulate according to the invention for the production of a molded body for shoe soles, parts of a shoe sole, for example shoe midsoles, shoe insoles, shoe combination soles, Bicycle saddles, bicycle tires, damping elements, upholstery, mattresses, underlays, handles, protective films, components in automobile interiors and exteriors, in balls and sports equipment or as floor coverings and wall coverings, especially for sports areas, athletic tracks, sports halls, children's playgrounds and sidewalks.
  • the subject matter of the invention is also the use of the expanded particles for the production of foams, and also foams obtainable from the expanded particles.
  • the present invention also relates to shaped bodies obtainable or obtained by the process according to the invention for producing a shaped body as described above.
  • the moldings according to the invention have a high elongation at break. Accordingly, according to a further embodiment, the present invention also relates to a shaped body as described above, wherein the shaped body has an elongation at break of greater than 100%, determined according to DIN EN ISO 1798.
  • thermoplastic elastomers (TPE-1) and (TPE-2) by using the composition (Z1) or the combination of the thermoplastic elastomers (TPE-1) and (TPE-2), it is also possible to produce moldings by means of steam welding using harder materials and thus, for example, to obtain moldings with a lower density , which are advantageous for applications, for example in the shoe sector.
  • thermoplastic elastomers (TPE-1) and (TPE-2) to set the material properties such as viscoelastic properties or stiffness in certain temperature ranges or the surface properties such as haptics and paintability in a targeted manner.
  • thermoplastic elastomers in particular thermoplastic polyurethanes (TPU), which cannot be obtained or produced in this way from one-component systems.
  • the combination of predominantly high-melting elastomer with a lower proportion of low-melting elastomer shows particular advantages in processing and weldability with steam and the production of molded parts.
  • the combination of predominantly low-melting elastomer with a lower proportion of high-melting elastomer shows special advantages in the low bulk density that can be achieved, which means a weight saving in a component and thus a cost and benefit advantage.
  • the particle foams according to the invention are particularly suitable for applications in the sports, shoe and comfort sectors.
  • the present invention also relates to the use of the foamed granules according to the invention or a foamed granules obtainable or obtained according to a method according to the invention for the production of shoe soles, bicycle saddles, bicycle tires, damping elements, padding, mattresses, underlays, handles, protective films, in components in the Automotive interiors and exteriors, in balls and sports equipment or as a floor covering, in particular for sports surfaces, athletics tracks, sports halls, children's playgrounds and sidewalks.
  • the foams according to the invention can be thermoplastically recycled without any problems.
  • the foamed materials are extruded using an extruder with a degassing device, where the extrusion can optionally be preceded by mechanical comminution. They can then be processed back into foams in the manner described above.
  • the shoe is preferably a street shoe, sports shoe, sandals, boots or safety shoe, particularly preferably a sports shoe.
  • a further object of the present invention is therefore also a shaped body, the shaped body being a combined shoe sole for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
  • a further object of the present invention is therefore also a shaped body, the shaped body being a midsole for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
  • a further object of the present invention is therefore also a shaped body, the shaped body being an insert for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
  • a further object of the present invention is therefore also a shaped body, the shaped body being a cushioning element for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
  • the padding element can be used in the heel area or forefoot area, for example.
  • Another subject of the present invention is therefore also a shoe in which the molded body according to the invention is used as a midsole, midsole or padding in the heel area, forefoot area, for example, the shoe preferably being a street shoe, sports shoe, sandal, boot or safety shoe, particularly preferably a sports shoe is.
  • the present invention also relates to a hybrid material containing a matrix made of a polymer (PM) and a foamed granulate according to the present invention.
  • a hybrid material containing a matrix made of a polymer (PM) and a foamed granulate according to the present invention.
  • Materials which comprise a foamed granulate and a matrix material are referred to as hybrid materials in the context of this invention.
  • the matrix material can consist of a compact material or also of a foam.
  • Polymers (PM) suitable as matrix material are known per se to those skilled in the art.
  • ethylene-vinyl acetate copolymers, epoxy-based binders or also polyurethanes are suitable within the scope of the present invention.
  • Polyurethane foams or also compact polyurethanes such as thermoplastic polyurethanes are suitable according to the invention.
  • the polymer (PM) is selected in such a way that there is sufficient adhesion between the foamed granules and the matrix in order to obtain a mechanically stable hybrid material.
  • the matrix can completely or partially surround the foamed granules.
  • the hybrid material can contain other components, for example other fillers or granules.
  • the hybrid material can also contain mixtures of different polymers (PM).
  • the hybrid material can also contain mixtures of foamed granules.
  • Foamed granules which can be used in addition to the foamed granules according to the present invention are known per se to those skilled in the art.
  • foamed granules of thermoplastic polyurethanes are suitable for the purposes of the present invention.
  • the present invention accordingly also relates to a hybrid material containing a matrix made from a polymer (PM), a foamed granulate according to the present invention and a further foamed granulate made from a thermoplastic polyurethane.
  • the matrix consists of a polymer (PM).
  • Suitable matrix materials in the context of the present invention are, for example, elastomers or foams, in particular foams based on polyurethanes, for example elastomers such as ethylene-vinyl acetate copolymers or also thermoplastic polyurethanes.
  • the present invention also relates to a hybrid material as described above, in which the polymer (PM) is an elastomer. Furthermore, the present invention relates to a hybrid material as described above, wherein the polymer (PM) is selected from the group consisting of ethylene-vinyl acetate copolymers and thermoplastic polyurethanes.
  • the present invention also relates to a hybrid material containing a matrix of an ethylene-vinyl acetate copolymer and a foamed granulate according to the present invention.
  • the present invention relates to a hybrid material containing a matrix made from an ethylene-vinyl acetate copolymer, a foamed granulate according to the present invention and another foamed granulate, for example made from a thermoplastic polyurethane.
  • the present invention relates to a hybrid material containing a matrix made of a thermoplastic polyurethane and a foamed granulate according to the present invention.
  • the present invention relates to a hybrid material containing a matrix made from a thermoplastic polyurethane, a foamed granulate according to the present invention and another foamed granulate, for example made from a thermoplastic polyurethane.
  • thermoplastic polyurethanes are known per se to those skilled in the art. Suitable thermoplastic polyurethanes are described, for example, in "Plastics Manual, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.
  • the polymer (PM) is preferably a polyurethane.
  • polyurethane includes all known elastic polyisocyanate polyaddition products. These include, in particular, solid polyisocyanate polyadducts, such as viscoelastic gels or thermoplastic polyurethanes, and elastic foams based on polyisocyanate polyadducts, such as flexible foams, semirigid foams or integral skin foams.
  • Solid polyisocyanate polyadducts such as viscoelastic gels or thermoplastic polyurethanes
  • elastic foams based on polyisocyanate polyadducts such as flexible foams, semirigid foams or integral skin foams.
  • Polyurethanes in the context of the invention mean elastic polymer blends containing polyurethanes and other polymers, and foams made from these polymer blends.
  • the matrix is a cured compact polyurethane binder, a resilient polyurethane foam, or a viscoelastic gel.
  • a polyurethane binder is understood to mean a mixture which consists of at least 50% by weight, preferably at least 80% by weight and in particular at least 95% by weight of a prepolymer containing isocyanate groups, hereinafter referred to as isocyanate prepolymer referred to, exists.
  • the viscosity of the polyurethane binder according to the invention is preferably in a range from 500 to 4000 mPa.s, particularly preferably from 1000 to 3000 mPa.s, measured at 25° C. according to DIN 53 018.
  • polyurethane foams are foams according to DIN 7726.
  • the density of the matrix material is preferably in the range from 1.2 to 0.01 g/cm 3 .
  • the matrix material is particularly preferably an elastic foam or an integral foam with a density in the range from 0.8 to 0.1 g/cm 3 , in particular from 0.6 to 0.3 g/cm 3 , or a compact material, for example a cured polyurethane binder.
  • Foams in particular are suitable as matrix material.
  • Hybrid materials that contain a matrix material made from a polyurethane foam preferably exhibit good adhesion between the matrix material and the foamed granules.
  • the present invention also relates to a hybrid material containing a matrix of a polyurethane foam and a foamed granulate according to the present invention.
  • the present invention relates to a hybrid material containing a matrix made from a polyurethane foam, a foamed granulate according to the present invention and another foamed granulate, for example made from a thermoplastic polyurethane.
  • the present invention relates to a hybrid material containing a matrix made of a polyurethane integral foam and a foamed granulate according to the present invention.
  • the present invention relates to a hybrid material containing a matrix made from a polyurethane integral foam, a foamed granulate according to the present invention and another foamed granulate, for example made from a thermoplastic polyurethane.
  • a hybrid material according to the invention containing a polymer (PM) as a matrix and foamed granules according to the invention, can be produced, for example, by mixing the components used to produce the polymer (PM) and the foamed granules, if appropriate with other components, and reacting them to form the hybrid material, the Reaction preferably takes place under conditions under which the foamed granules are essentially stable.
  • Suitable processes and reaction conditions for preparing the polymer (PM), in particular an ethylene-vinyl acetate copolymer or a polyurethane, are known per se to those skilled in the art.
  • the hybrid materials according to the invention are integral skin foams, in particular integral skin foams based on polyurethanes.
  • integral skin foams are preferably produced by the one-shot process using low-pressure or high-pressure technology in closed, suitably temperature-controlled molds.
  • the molds are usually made of metal, such as aluminum or steel.
  • the amount of reaction mixture introduced into the mold is such that the moldings obtained from integral foams have a density of 0.08 to 0.70 g/cm 3 , in particular 0.12 to 0.60 g/ cm3 .
  • the degrees of compaction for producing the shaped bodies with a compacted edge zone and a cellular core are in the range from 1.1 to 8.5, preferably from 2.1 to 7.0.
  • hybrid materials with a matrix of a polymer (PM) and the foamed granules according to the invention contained therein, in which there is a homogeneous distribution of the foamed particles.
  • the foamed granules according to the invention can easily be used in a process for producing a hybrid material, since the individual particles are free-flowing due to their small size and do not place any special demands on processing. Techniques for homogeneous distribution of the foamed granules, such as slow rotation of the mold, can be used.
  • auxiliaries and/or additives can also be added to the reaction mixture for the production of the hybrid materials according to the invention. Mention may be made, for example, of surface-active substances, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, hydrolysis inhibitors, odor-absorbing substances and fungistatic and bacteriostatic substances.
  • Suitable surface-active substances are, for example, compounds which serve to support the homogenization of the starting materials and may also be suitable for regulating the cell structure.
  • emulsifiers such as the sodium salts of castor oil sulfates or fatty acids, and salts of fatty acids with amines, for example diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate, salts of sulfonic acids, for example alkali metal or ammonium salts of dodecylbenzene or dinaphthylmethanedisulfonic acid and ricinoleic acid;
  • Foam stabilizers such as siloxane-oxyalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or.
  • ricinoleic acid esters Turkish red oil and peanut oil, and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes.
  • Oligomeric acrylates with polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving the emulsifying effect, the cell structure and/or stabilizing the foam.
  • suitable release agents are: reaction products of fatty acid esters with polyisocyanates, salts of amino-containing polysiloxanes and fatty acids, salts of saturated or unsaturated (cyclo)aliphatic carboxylic acids having at least 8 carbon atoms and tertiary amines and, in particular, internal release agents such as carboxylic acid esters and/or -amides, prepared by esterification or amidation of a mixture of montanic acid and at least one aliphatic carboxylic acid having at least 10 carbon atoms with at least difunctional alkanolamines, polyols and/or polyamines with molecular weights of 60 to 400 g/mol, mixtures of organic amines, metal salts of Stearic acid and organic mono and/or dicarboxylic acids or their anhydrides or mixtures of an imino compound, the metal salt of a carboxylic acid and optionally a carboxylic acid.
  • Fillers in particular fillers with a reinforcing effect, are to be understood as meaning the customary organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating agents, etc. which are known per se.
  • inorganic fillers such as silicate minerals, for example phyllosilicates such as antigorite, bentonite, serpentine, hornblende, amphibole, chrisotile, talc
  • Metal oxides such as kaolin, aluminum oxide, titanium oxide, zinc oxide and iron oxide, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide, zinc sulfide and glass, etc.
  • kaolin china clay
  • aluminum silicate and co-precipitates of barium sulfate and aluminum silicate as well as natural and synthetic fibrous Minerals such as wollastonite, metal and in particular glass fibers of various lengths, which may or may not be sized.
  • Suitable organic fillers are, for example: carbon black, melamine, rosin, cyclopentadienyl resins and graft polymers and cellulose fibers, polyamide, polyacrylonitrile, polyurethane and polyester fibers based on aromatic and/or aliphatic dicarboxylic acid esters and in particular carbon fibers.
  • the inorganic and organic fillers can be used individually or as mixtures.
  • the volume fraction of the foamed granules is preferably 20 percent by volume and more, particularly preferably 50 percent by volume and more preferably 80 percent by volume and more and in particular 90 percent by volume and more, based in each case on the volume of the hybrid system according to the invention.
  • hybrid materials according to the invention are characterized by very good adhesion of the matrix material to the foamed granulate according to the invention.
  • a hybrid material according to the invention preferably does not tear at the interface between matrix material and foamed granules. This makes it possible to produce hybrid materials which, with the same density, have improved mechanical properties, such as tear propagation resistance and elasticity, compared to conventional polymer materials, in particular conventional polyurethane materials.
  • the elasticity of hybrid materials according to the invention in the form of integral foams is preferably greater than 40% and particularly preferably greater than 50% according to DIN 53512.
  • hybrid materials according to the invention in particular those based on integral foams, show high rebound resilience at low density.
  • integral skin foams based on hybrid materials according to the invention are therefore outstandingly suitable as materials for shoe soles. As a result, light and comfortable soles with good durability properties are obtained. Such materials are particularly suitable as midsoles for sports shoes.
  • hybrid materials according to the invention with a cellular matrix are suitable, for example, for padding, for example of furniture, and mattresses.
  • Hybrid materials with a matrix of viscoelastic gel are characterized by increased viscoelasticity and improved elastic properties. These materials are therefore also suitable as upholstery materials, for example for seats, especially saddles such as bicycle saddles or motorcycle saddles.
  • Hybrid materials with a compact matrix are suitable, for example, as floor coverings, in particular as coverings for playgrounds, athletic tracks, sports fields and sports halls.
  • the properties of the hybrid materials according to the invention can vary widely depending on the polymer (PM) used and can be achieved in particular by varying the size, shape and nature of the expanded granules, or by adding other additives, for example other non-foamed granules such as plastic granules, for example rubber granules, can be varied within wide limits.
  • hybrid materials according to the invention have a high level of durability and resilience, which is particularly evident in the high tensile strength and elongation at break.
  • hybrid materials according to the invention have a low density.
  • the present invention also includes those embodiments that result from the back-references given below and combinations thereof.
  • the present invention also includes those embodiments that result from the back-references given below and combinations thereof.
  • a range of embodiments is mentioned, for example in connection with the phrase “according to any one of embodiments (1) to (4)”, each of the embodiments in that range is intended to be explicitly disclosed.
  • the wording is considered to be synonymous for the person skilled in the art with the expression “according to one of the embodiments (1), (2), (3) and (4)”. It is explicitly stated that the following embodiments do not constitute the patent claims, but rather a structured part of the description concerning general and preferred aspects of the present invention.
  • An embodiment (1) of the present invention relates to a foamed granulate consisting of a composition (Z1), wherein the composition contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer ( TPE-2).
  • TPE-1 thermoplastic elastomer
  • TPE-2 thermoplastic elastomer
  • a further preferred embodiment (2) which specifies embodiment (1), relates to the foamed granules from a composition (Z1) according to embodiment (1), wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, thermoplastic copolyester elastomers, polyetheresters, polyesteresters or thermoplastic styrene butadiene block copolymers.
  • TPE-1 thermoplastic elastomer
  • thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, or thermoplastic copolyester elastomers.
  • Another preferred embodiment (4) which substantiates embodiments (1) to (3), relates to the foamed granules of a composition (Z1) according to one of embodiments (1) to (3), wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane.
  • thermoplastic elastomer (TPE-2) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters or thermoplastic styrene butadiene block copolymers.
  • Another preferred embodiment (6) which substantiates embodiments (1) to (5), relates to the foamed granules of a composition (Z1) according to one of embodiments (1) to (5), wherein the thermoplastic elastomer (TPE-2) has a hard segment content of less than 25%.
  • a further preferred embodiment (7) which substantiates embodiments (1) to (6), relates to the foamed granules from a composition (Z1) according to one of embodiments (1) to (6), the closed-cell content of the foam being greater than 60% is determined according to DIN ISO 4590:2016.
  • Another preferred embodiment (8) which substantiates embodiments (1) to (7), relates to the foamed granules of a composition (Z1) according to one of embodiments (1) to (7), the particles being determined at the narrowest point have an average diameter in the range from 1 mm to 20 mm, measured using a graduated microscope.
  • a further preferred embodiment (9) of the invention relates to a method for producing a foamed granulate, preferably according to one of the embodiments (1) to (8), comprising the steps
  • composition (i) providing a composition (Z1) in the form of granules, the composition containing at least one thermoplastic elastomer (TPE-1). a Shore D hardness in the range of 20 to 90 and a second thermoplastic elastomer (TPE-2);
  • step (ii) producing a foamed granulate from the granulate provided according to step (i).
  • thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, thermoplastic copolyester elastomers, polyether esters , polyester esters or thermoplastic styrene butadiene block copolymers.
  • thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes , thermoplastic polyetheramides, or thermoplastic copolyester elastomers.
  • thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane.
  • thermoplastic elastomer (TPE-2) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters or thermoplastic styrene butadiene block copolymers.
  • thermoplastic elastomer (TPE-2) has a hard segment content of less than 25% having.
  • Another preferred embodiment (15), which substantiates embodiments (9) to (14), relates to the method according to one of embodiments (9) to (14), wherein the closed cell content of the foam is greater than 60%, determined according to DIN ISO 4590 :2016.
  • Another preferred embodiment (16), which specifies embodiments (9) to (15), relates to the method according to one of embodiments (9) to (15), the particles having an average diameter in the range of 1 mm at the narrowest point up to 20 mm, measured using a scale microscope.
  • a further preferred embodiment (17) of the invention relates to a method for producing a shaped body comprising the steps (a) Providing foamed granules, preferably foamed granules according to one of embodiments (1) to (8), consisting of a composition (Z1), wherein the composition comprises at least one thermoplastic elastomer (TPE-1) with a Shore D hardness of im range of 20 to 90 and a second thermoplastic elastomer (TPE-2);
  • step (b) Production of a shaped body from the foamed granulate provided according to step (a).
  • thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, thermoplastic copolyester elastomers, polyether esters , polyester esters or thermoplastic styrene butadiene block copolymers.
  • thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, or thermoplastic copolyester elastomers.
  • thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane.
  • thermoplastic elastomer (TPE-2) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters or thermoplastic styrene butadiene block copolymers.
  • thermoplastic elastomer (TPE-2) has a hard segment content of less than 25% having.
  • Another preferred embodiment (23), which substantiates embodiments (17) to (22), relates to the method according to one of embodiments (17) to (22), wherein the closed cell content of the foam is greater than 60%, determined according to DIN ISO 4590 :2016.
  • Another preferred embodiment (24), which specifies embodiments (17) to (23), relates to the method according to one of embodiments (17) to (23), the particles having an average diameter in the range of 1 mm at the narrowest point up to 20 mm, measured using a scale microscope.
  • a further preferred embodiment (25), which specifies embodiments (17) to (24), relates to the method according to one of the embodiments (17) to (24), wherein the production of the shaped body according to step (b) by means of welding the according to step ( a) provided particles by means of steam, hot air or high-energy radiation.
  • a further preferred embodiment (26) of the invention relates to a shaped body obtainable or obtained by a process according to embodiment (9) or (17).
  • a further preferred embodiment (27) of the invention relates to a shaped body obtainable or obtained by a method comprising the steps
  • (a) Providing foamed granules, preferably foamed granules according to one of embodiments (1) to (8), consisting of a composition (Z1), wherein the composition comprises at least one thermoplastic elastomer (TPE-1) with a Shore D hardness of im range of 20 to 90 and a second thermoplastic elastomer (TPE-2);
  • TPE-1 thermoplastic elastomer
  • TPE-2 thermoplastic elastomer
  • step (b) Production of a shaped body from the foamed granulate provided according to step (a).
  • Another preferred embodiment (28), which specifies one of the embodiments (26) or (27), relates to a shaped body according to one of the embodiments (26) or (27), wherein the shaped body has an elongation at break of greater than 100%, determined according to DIN EN ISO 1798.
  • Another preferred embodiment (29), which specifies one of the embodiments (26) to (28), relates to a shaped body according to one of the embodiments (26) to (28), wherein the shaped body is a shoe sole, bicycle saddle, bicycle tire, damping element, padding, Mattress, underlay, handle, protective film, a component in the automotive interior and exterior, a ball and sports equipment or a floor covering, in particular for sports areas, athletics tracks, sports halls, children's playgrounds and sidewalks.
  • Another preferred embodiment (30) of the invention relates to the use of foamed granules according to one of embodiments (1) to (8) or foamed granules obtainable or obtained by a process according to one of embodiments (9) to (16) for the production of Shoe soles, bicycle saddles, bicycle tires, damping elements, upholstery, mattresses, underlays, handles, protective films, in components for automotive interiors and exteriors, in balls and sports equipment or as floor coverings, especially for sports surfaces, athletic tracks, sports halls, children's playgrounds and sidewalks.
  • TPU1 TPU based on MDI, butanediol, polytetrahydrofuran Mn 1000g/mol with a shore hardness of 70A
  • TPU2 TPU based on MDI, butanediol, polytetrahydrofuran Mn 1000g/mol with a shore hardness of 80A
  • TPU3 TPU based on MDI, butanediol, polytetrahydrofuran Mn 1000g/mol with a shore hardness of 90A
  • TPA polyetheramide based on a flexible polytetrahydrofuran and crystalline polyamide units from Arkema, Shore 82A (Pebax 3533)
  • thermoplastic elastomers (Table 1) are mixed and melted in a twin-screw extruder with a screw diameter of 44 mm and a length-to-diameter ratio of 42.
  • blowing agent After melting, a mixture of CO2 (2 parts by weight) and N2 (0.2 parts by weight) was added as blowing agent. When passing through the remaining extruder section, the blowing agent and the polymer melt were mixed with one another so that a homogeneous mixture was formed.
  • the melt mixture was then pressed into a perforated plate (LP) by means of a gear pump (ZRP) via a starter valve with screen changer (AV) and in the cutting chamber of the underwater granulation (UWG) to form granules (25 mg). cut and carried away with the tempered and pressurized water, thereby expanding. After the expanded granules have been separated from the water by means of a centrifugal dryer, the expanded granules are dried at 60° C. for 3 hours.
  • the temperatures used for the plant components are listed in Table 2 for the blends.
  • the bulk densities of the expanded granules resulting for the individual blends are listed in Table 3.
  • the bulk density is measured analogously to DIN ISO 697, whereby when determining the above values, in contrast to the standard, a vessel with a volume of 10 l is used instead of a vessel with a volume of 0.5 l, since this is especially the case with the foam particles with a low density and large mass a measurement with only 0.5 l volume is too imprecise.
  • the expanded granules were then welded on a molding machine from Kurtz ersa GmbH (Boost Foamer) to form square sheets with a side length of 200 mm and a thickness of 10 mm or 20 mm by exposure to steam.
  • the welding parameters differ only with regard to the cooling.
  • the welding parameters of the different materials were chosen in such a way that the plate side of the final molded part, which faced the moving side (mil) of the tool, had the lowest possible number of collapsed ETPU particles. If necessary, the gap vaporization also took place through the movable side of the tool. It was not always possible to obtain a satisfactory surface finish in the comparative examples. Irrespective of the experiment, a cooling time of 120 s for a plate thickness of 20 mm and 100 s for a 10 mm thick plate was always set at the end of the fixed (M1) and the moving side of the tool.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention se rapporte à un matériau granulaire expansé constitué d'une composition (Z1), la composition contenant au moins un élastomère thermoplastique (TPE-1) présentant une dureté Shore D dans la plage de 20 à 90 et un second élastomère thermoplastique (TPE-2). L'invention se rapporte également à un procédé de préparation d'une mousse particulaire granulaire expansée de ce type, et à un procédé de préparation d'un article façonné à partir du matériau granulaire expansé, et à l'utilisation du matériau granulaire expansé selon l'invention pour produire des semelles de chaussure, des selles de bicyclette, des pneus de bicyclette, des éléments amortisseurs, un amortissement, des matelas, un rembourrage, des éléments de préhension, des films protecteurs, dans des composants pour intérieurs et extérieurs automobiles, dans des balles et des équipements sportifs ou comme revêtement de sol, en particulier pour des surfaces de sport, des pistes d'athlétisme, des salles de sport, des revêtements de sol et des aires de jeu pour enfants.
PCT/EP2022/051856 2021-01-28 2022-01-27 Mousse particulaire à base de tpe présentant une dureté shore a comprise entre 20d et 90d WO2022162048A1 (fr)

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WO2024089365A1 (fr) 2022-10-26 2024-05-02 Arkema France Mousse de polyuréthane thermoplastique et de copolymère à blocs polyamides et à blocs polyéthers
WO2024089363A1 (fr) 2022-10-26 2024-05-02 Arkema France Mousse de polyuréthane thermoplastique et polyamide
WO2024089364A1 (fr) 2022-10-26 2024-05-02 Arkema France Mousse de polyuréthane thermoplastique et de copolymère à blocs polyamides et à blocs polyéthers à bouts de chaîne amines

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WO2024089365A1 (fr) 2022-10-26 2024-05-02 Arkema France Mousse de polyuréthane thermoplastique et de copolymère à blocs polyamides et à blocs polyéthers
WO2024089363A1 (fr) 2022-10-26 2024-05-02 Arkema France Mousse de polyuréthane thermoplastique et polyamide
WO2024089364A1 (fr) 2022-10-26 2024-05-02 Arkema France Mousse de polyuréthane thermoplastique et de copolymère à blocs polyamides et à blocs polyéthers à bouts de chaîne amines
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FR3141466A1 (fr) 2022-10-26 2024-05-03 Arkema France Mousse de polyuréthane thermoplastique et polyamide
FR3141465A1 (fr) 2022-10-26 2024-05-03 Arkema France Mousse de polyuréthane thermoplastique et de copolymère à blocs polyamides et à blocs polyéthers à bouts de chaîne amines

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