Classifications

• • 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
  • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2101/00—Manufacture of cellular products
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2410/00—Soles
• • 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
  • C08J2207/00—Foams characterised by their intended use
• • 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
  • 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

Definitions

• the present invention relates to foamed granules comprising a thermoplastic polyurethane obtainable or obtained by reacting a polyisocyanate composition (IZ) which contains at least one aliphatic diisocyanate with a number average molecular weight less than 200 g / mol, at least one chain extender (KV1), and one
• IZ polyisocyanate composition
• KV1 chain extender
• the present invention further comprises the use of a foamed granulate according to the invention for the production of a shaped body.
• Polyisocyanate composition (IZ), a chain extender (KV1) and one
• the isocyanate composition (IZ) contains an aliphatic diisocyanate with a number average molecular weight less than 200 g / mol. Suitable isocyanates are known per se to the person skilled in the art. According to the invention, the isocyanate composition (IZ) can also contain further isocyanates.
• the aliphatic isocyanate is preferably a linear diisocyanate, in particular a linear diisocyanate with an even number of carbon atoms.
• the present invention accordingly relates to a foamed granulate as described above, the aliphatic diisocyanate being a linear diisocyanate with an even number of carbon atoms.
• the aliphatic diisocyanate is more preferably isomerically pure in the context of the present invention.
• a suitable aliphatic diisocyanate with a number average molecular weight less than 200 g / mol is, for example, flexamethylene diisocyanate (HDI).
• the present invention accordingly relates to a foamed granulate as described above, the aliphatic diisocyanate
• Flexamethylene diisocyanate (Fl Dl) is.
• Suitable further isocyanates in the context of the present invention are, in particular, diisocyanates, in particular aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates.
• pre-reacted products can be used as the isocyanate component, in which some of the OH components are reacted with an isocyanate in a preceding reaction step. The products obtained are reacted with the remaining OH components in a subsequent step, the actual polymer reaction, and then form the
• thermoplastic polyurethane thermoplastic polyurethane
• Aliphatic and / or cycloaliphatic are customary aliphatic diisocyanates
• Diisocyanates used, for example tri-, tetra-, penta-, hexa-, hepta- and / or
• Octamethylene diisocyanate 2-methylpentamethylene-1, 5-diisocyanate, 2-ethyltetramethylene-1, 4-diisocyanate, butylene-1, 4-diisocyanate, trimethylhexamethylene-1, 6-diisocyanate, 1-isocyanato-3,3,5-trimethyl- 5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, 1-methyl-2,4- and / or 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-, 2,4'- and / or 2,2'-methylene dicyclohexyl diisocyanate (H12MDI).
• 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), methylene diphenyl diisocyanate (MDI), the term MDI being understood to mean 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate , 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate or H12MDI (4,4'-methylene dicyclohexyl diisocyanate).
• NDI 1,5-nap
• biuretas of the aforementioned diisocyanates furthermore oligomers which are obtainable by the targeted reaction of semiblocked diisocyanates with polyols which on average have more than two and preferably three or more hydroxyl groups.
• the amount of crosslinker i.e.
• the polyisocyanate composition can also contain one or more solvents.
• suitable solvents are known to the person skilled in the art.
• non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons are suitable.
• a polyol composition (PZ) is used.
• the polyol composition (PZ) contains at least one polyol. Suitable polyols are
• polyesterol or polyetherol are particularly preferably used as polyol (P1).
• Polycarbonates can also be used.
• Copolymers can also be used in the context of the present invention.
• the number average molecular weight of the polyols used according to the invention are preferably in the range from 500 and 5000 g / mol, for example in the range from 550 g / mol and 2000 g / mol, preferably in the range from 600 g / mol and 1500 g / mol, in particular between 650 g / mol and 1000 g / mol.
• polyether films are suitable, but also polyester films, block copolymers and hybrid polyols such as e.g. Poly (ester / amide).
• preferred polyetherols are polyethylene glycols, polypropylene glycols, polyadipates, polycarbonate (diols) and polycaprolactone.
• the present invention accordingly relates to a foamed granulate as described above, the polyol composition being a polyol selected from the group consisting of polyether, polyester,
• Suitable polyols are, for example, those which have ethers and ester blocks, such as, for example, polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or else polyether with polycaprolactone end blocks.
• preferred polyetherols are polyethylene glycols, polypropylene glycols. Polycaprolactone is also preferred.
• the polyols or the polyol composition used preferably have an average functionality between 1.8 and 2.3, preferably between 1.9 and 2.2, in particular 2.
• polyethers are suitable as further polyols, for example, but also polyesters, block copolymers and hybrid polyols such as e.g. Poly (ester / amide). Suitable
• Block copolymers are, for example, those which have ethers and ester blocks, such as, for example, polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or else polyethers with polycaprolactone end blocks.
• preferred polyetherols are polyethylene glycols, polypropylene glycols. Also preferred as a further polyol
• composition of the polyol composition can vary within a wide range in the context of the present invention.
• the polyol composition can also contain mixtures of different polyols.
• the polyol composition can also contain a solvent.
• Suitable solvents are known per se to the person skilled in the art.
• the number average molecular weight Mn of the polytetrahydrofuran is preferably in the range from 500 to 5000 g / mol.
• the number average molecular weight Mn of the polytetrahydrofuran is more preferably in the range from 500 to 1400 g / mol.
• the present invention also relates to foamed granules as described above, the polyol composition comprising a polyol selected from the group consisting of polytetrahydrofurans with a number average molecular weight Mn in the range from 500 g / mol to 5000 g / mol.
• the present invention accordingly relates to a foamed granulate as described above, the polyol composition
• the polyol composition comprising a polyol selected from the group consisting of polytetrahydrofurans with a number average molecular weight Mn in the range from 500 g / mol to 2000 g / mol.
• Mixtures of different polytetrahydrofurans can also be used according to the invention, i.e. Mixtures of polytetrahydrofurans with different molecular weights.
• preferred polyether glycols are polyethylene glycols, polypropylene glycols and polytetrahydrofurans, and also their mixed polyether glycols.
• mixtures of different polytetrahydrofurans can also be used, which are in the
• Invention are particularly preferably 1, 2-ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-flexanediol.
• 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 or 1,4- Cyclohexanediol are suitable in the context of the present invention as chain extenders (KV1).
• KV1 chain extenders
• the present invention accordingly relates to a foamed granulate as described above, the chain extender (KV1) being selected is from the group consisting of 1,3-propanediol, 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol and HQEE.
• the chain extender (KV1) being selected is from the group consisting of 1,3-propanediol, 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol and HQEE.
• the proportions of the components used are preferably selected in accordance with step (b) in such a way that a hard segment content in the range from 10 to 40% is obtained.
• the weight-average molecular weights Mw of the thermoplastic block copolymers, dissolved in HFIP (hexafluoroisopropanol), are determined by means of GPC in the context of the present invention.
• the molecular weight is determined using two GPC columns connected in series (PSS-Gel; 100A; 5m; 300 * 8mm, Jordi-Gel DVB; MixedBed; 5m; 250 * 10mm; column temperature 60 ° C; flow 1 mL / min; Rl- Detector).
• the calibration is carried out with polymethyl methacrylate (EasyCal; PSS, Mainz), HFIP is used as the solvent.
• the present invention also relates to a method for producing a foamed granulate.
• the present invention relates to a
• a method for producing a foamed granulate comprising the steps
• thermoplastic polyurethane obtained or obtainable Reaction of at least components (a) to (c):
• Polymer mixture of the composition (Z1) is known from the Individual components and optionally further components such as, for example
• compatibilizers or auxiliaries such as stabilizers
• auxiliaries such as stabilizers
• the components are all metered into the feed and conveyed together into the extruder, or individual components are added via a side metering.
• the foamed granules 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 amount of blowing agent is preferably 0.1 to 40, in particular 0.5 to 35 and particularly preferably 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
• the non-expanded granulate preferably has an average minimum diameter of 0.2-10 mm (determined via 3D evaluation of the granulate, e.g. via dynamic image analysis using an optical measuring device called PartAn 3D from Microtrac).
• step (I) can take place in the presence of water and optionally suspension auxiliaries or only in the presence of the blowing agent and
• Suitable suspension auxiliaries are, for example, water-insoluble inorganic stabilizers, such as tricalcium phosphate, magnesium pyrophosphate, metal carbonates; also polyvinyl alcohol and surfactants, such as sodium dodecylaryl sulfonate. 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 from 100 ° C. to 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
• Impregnation time is generally 0.5 to 10 hours.
• Suitable blowing agents for carrying out the process in a suitable closed reaction vessel are e.g. organic liquids and gases used in the
• Processing conditions are in a gaseous state, such as hydrocarbons or inorganic gases or mixtures of organic liquids or gases and inorganic gases, which can also be combined.
• Suitable hydrocarbons are, for example, 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, in particular those with 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 above-mentioned gases.
• the impregnation of the granules with a blowing agent under pressure comprises the process and subsequent expansion of the granules in steps (a) and (ß):
• Suitable blowing agents in this process variant are volatile organic compounds with a boiling point at normal pressure of 1013 mbar from -25 ° C to 150 ° C, in particular -10 ° C to 125 ° C.
• Hydrocarbons preferably halogen-free
• C4-10- Alkanes for example the isomers of butane, pentane, hexane, heptane and octane, particularly preferably isobutane.
• Other possible blowing agents are more sterically demanding compounds such as alcohols, ketones, esters, ethers and organic carbonates
• composition in step (ii) is mixed in an extruder while melting with the blowing agent under pressure, which is fed to the extruder.
• blowing agent mixture is under pressure, preferably with a moderately controlled
• Single-screw and twin-screw extruders e.g. type ZSK from Werner & Pfleiderer
• co-kneaders e.g. type ZSK from Werner & Pfleiderer
• Kombiplast machines MPC kneading mixers
• FCM mixers KEX kneading screw extruders
• shear roller extruders such as those e.g. in Saechtling (ed.), plastic paperback, 27.
• 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. to 250 ° C., in particular 150 to 210 ° C. and a pressure after the blowing agent has been added of 40 to 200 bar, preferably 60 to 150 bar, particularly preferably 80 to 120 bar in order to ensure homogenization of the blowing agent with the melt.
• a first extruder for example, in a first extruder
• Components are melted and blinded, and a blowing agent is injected.
• the impregnated melt is homogenized and the temperature and or the pressure are adjusted. If, for example, three extruders are combined with one another, the mixing of the components and the injection of the blowing agent can also be divided into two different process parts. If, as is preferred, only one extruder is used, all process steps, melting, mixing, injection of the
• Blowing agent homogenization and adjusting the temperature and or the pressure carried out in an extruder.
• the corresponding, possibly even already colored, foamed granules can be produced directly from the granules in that the corresponding granules are coated with a
• Suitable supercritical liquids 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 liquid can also contain a polar liquid with a Flildebrand solubility parameter equal to or greater than 9 MPa-1/2.
• the supercritical fluid or the heated fluid may also contain a dye, whereby a colored, foamed article is obtained.
• Another object of the present invention is a molded article produced from the foamed granules according to the invention.
• the fixing position of the corresponding shaped bodies can be known according to the person skilled in the art
• a preferred method for locating a foam molded part comprises the following steps:
• step (B) Fusion of the foamed granules according to the invention from step (i).
• the fusion in step (B) is preferably carried out in a closed form, the fusion being able to take place by means of water vapor, industrial air (as described for example in EP1979401 B1) or energetic radiation (microwaves or radio waves).
• the temperature at which the foamed granules are fused is preferably below or close to the melting temperature of the polymer from which the particle foam was produced.
• the temperature for fusing the foamed granules is between 100 ° C and 180 ° C, preferably between 120 and 150 ° C.
• temperature profiles / dwell times can be determined individually, e.g. in analogy to the methods described in US20150337102 or EP2872309B1.
• the welding via energetic radiation generally takes place in the frequency range of microwaves or radio waves, possibly in the presence of water or other polar liquids, such as e.g. microwave-absorbing polar groups
• Hydrocarbons such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols
• Hydrocarbons can be analogous to those in EP3053732A or
• the foamed granules can also contain dyes. Dyes can be added in various ways.
• the foamed granules produced can be colored after production.
• the corresponding foamed granules are contacted with a carrier liquid containing a dye, the carrier liquid (TF) having a polarity that is suitable for sorption of the carrier liquid into the foamed granulate.
• TF carrier liquid
• Suitable dyes are, for example, inorganic or organic pigments.
• Suitable natural or synthetic inorganic pigments are, for example, carbon black, graphite,
• Suitable organic pigments are, for example, azo pigments and polycyclic pigments.
• the color can be added during the production of the foamed granulate.
• the dye can be added to the extruder in the production of the foamed granules by extrusion.
• already colored material can be used as the starting material for the production of the foamed granulate, which is extruded or - expanded in a closed vessel according to the above-mentioned methods.
• the supercritical liquid or the heated liquid can contain a dye.
• the molded parts 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 molded articles 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) and the compressive stress is above 15 kPa at 10% compression (analogous to DIN EN ISO 844, November 2014; the deviation from the norm lies in the height of the sample with 20 mm instead of 50 mm and thus the adjustment of the test speed to 2 mm / min ).
• Test specimen height which should be 12 mm, but is carried out with 20 mm in this test in order to avoid “strikethrough” the sample and measuring the substrate).
• the density of the molded parts produced is advantageously between 75 to 375 kg / m 3 , preferably between 100 to 300 kg / m 3 , particularly preferably between 150 to 200 kg / m 3 (DIN EN ISO 845, October 2009).
• foamed granules are generally between 1.5 and 2.5, preferably between 1.8 and 2.0.
• the invention further relates to the use of an inventive
• foamed granulate for the production of a molded article for shoe midsoles, shoe insoles, shoe combination soles, bicycle saddles, bicycle tires, damping elements, upholstery, mattresses, underlays, handles, protective films, in components in the interior and exterior of automobiles, in balls and sports equipment or as flooring, in particular for sports surfaces , Track and field tracks, sports halls, children's playgrounds and sidewalks.
• the shoe is preferably a street shoe, sports shoe, sandals, boots or safety shoe, particularly preferably a sports shoe.
• the present invention accordingly also relates to a molded body, the molded body being a shoe combination sole for shoes, preferably for street shoes,
• Sports shoes sandals, boots or safety shoes, particularly preferred sports shoes.
• the present invention accordingly also relates to a molded article, the molded article being an midsole for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
• the present invention accordingly also relates to a molded article, the molded article being an insert for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
• the present invention accordingly also relates to a molded article, the molded article 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 e.g. be used in the heel area or forefoot area.
• Another object of the present invention is therefore also a shoe in which the molded body according to the invention as a midsole, midsole or cushioning in, for example Heel area, forefoot area is used, the shoe preferably a
• the present invention also relates to foamed granules obtained or obtainable by a process according to the invention.
• the block copolymers used according to the invention usually have a hard phase made of aromatic polyester and a soft phase.
• the block copolymers used according to the invention have a good phase separation between the elastic soft phase and the rigid hard phase due to their predetermined block structure, which results from the structure of inherently polymeric and thus long-chain molecules such as a polytetrahydrofuran and a polybutylene terephthalate building block.
• This good phase separation manifests itself in a property which is referred to as high, snappiness, but which is very difficult to characterize with physical methods and which is particularly advantageous
• the polymer foams according to the invention are particularly suitable for the production of moldings. Moldings can be produced from the foamed granules according to the invention, for example by welding or gluing.
• the present invention also relates to the use of a foamed granulate according to the invention or of a foamed granulate obtained or obtainable by a process according to the invention for the production of moldings.
• the present invention also relates to the use of a foamed granulate according to the invention or of a foamed granulate obtained or obtainable by a process according to the invention for the production of molded articles, the molded article being produced by welding or gluing the particles together.
• the moldings obtained according to the invention are suitable, for example, for the production of shoe soles, parts of a shoe sole, bicycle saddles, upholstery, mattresses, underlays, handles, protective films, components in the interior and exterior of automobiles, in balls and
• Sports equipment or as flooring and wall cladding in particular for sports areas, athletic tracks, sports halls, children's playgrounds and sidewalks.
• the present invention also relates to the use of a foamed granulate according to the invention or of a foamed granulate obtained or obtainable by a method according to the invention for the production of molded articles, the molded article being a shoe sole, part of a shoe sole Bicycle saddle, an upholstery, a mattress, pad, handle, protective film, a component in the automotive interior and exterior.
• the present invention also relates to the use of the foamed granules or foamed particles according to the invention in balls and sports equipment or as flooring and wall covering, in particular for sports areas, athletic tracks, sports halls, children's playgrounds and walkways.
• 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 comprising 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 the person skilled in the art.
• ethylene-vinyl acetate copolymers, epoxy-based binders or even polyurethanes are suitable in the context of the present invention.
• Polyurethane foams or compact polyurethanes such as, for example, are suitable according to the invention
• thermoplastic polyurethanes are thermoplastic polyurethanes.
• the polymer (PM) is selected such 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 granulate.
• the hybrid material can contain further components, for example further fillers or granules.
• the hybrid material can also contain mixtures of different polymers (PM).
• the hybrid material can too
• Foamed granules which can be used in addition to the foamed granules according to the present invention are known per se to the person skilled in the art. Foamed granules made of thermoplastic polyurethanes are particularly suitable for the purposes of the present invention.
• the present invention accordingly also relates to a
• Hybrid material containing a matrix of a polymer (PM), a foamed granulate according to the present invention and a further foamed granulate made of a thermoplastic polyurethane.
• the matrix consists of a polymer (PM).
• Elastomers or, for example, are suitable as matrix material in the context of the present invention
• the present invention also relates to a hybrid material as described above, wherein the polymer (PM) is an elastomer. Furthermore, the present invention relates to a hybrid material as described above, the polymer (PM) being 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 of an ethylene-vinyl acetate copolymer, a foamed granulate according to the present invention and a further foamed granulate, for example made of 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 of a thermoplastic polyurethane, a foamed granulate according to the present invention and a further foamed granulate, for example made of a thermoplastic polyurethane.
• thermoplastic polyurethanes are known per se to the person skilled in the art. Suitable thermoplastic polyurethanes are described, for example, in "Kunststoff Handbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 3.
• the polymer (PM) is preferably a polyurethane.
• Polyurethane in the sense of the invention includes all known elastic polyisocyanate polyaddition products. These include, in particular, massive polyisocyanate polyadducts, such as viscoelastic gels or thermoplastic polyurethanes, and elastic foams based on polyisocyanate polyadducts, such as
• polyurethanes are to be understood as meaning elastic polymer blends containing polyurethanes and other polymers, and foams made from these polymer blends.
• the matrix is preferably a hardened, compact polyurethane binder, an elastic polyurethane foam or a viscoelastic gel.
• a polyurethane binder is understood to be a mixture which comprises 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.
• 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.
• the density of the matrix material is preferably in the range from 1.2 to 0.01 g / cm 3.
• Hybrid materials that contain a matrix material made of a polyurethane foam preferably have good adhesion between the matrix material and the foamed granulate.
• the present invention also relates to a hybrid material containing a matrix made 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 of a polyurethane foam, a foamed granulate according to the present invention and a further foamed granulate, for example made of a thermoplastic polyurethane.
• the present invention relates to a hybrid material containing a matrix 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 of an integral polyurethane foam, a foamed granulate according to the present invention and a further foamed granulate, for example made of a thermoplastic polyurethane.
• a hybrid material according to the invention containing a polymer (PM) as a matrix and a foamed granulate according to the invention can be produced, for example, by mixing the components used to produce the polymer (PM) and the foamed granulate, if appropriate, with other components and converting them to the hybrid material, the The reaction is preferably carried out under conditions under which the foamed granulate is essentially stable.
• Suitable processes and reaction conditions for producing the polymer (PM), in particular an ethylene-vinyl acetate copolymer or a polyurethane, are known per se to the person skilled in the art.
• the hybrid materials according to the invention are integral foams, in particular integral foams based on polyurethanes.
• Suitable processes for producing integral foams are known per se to the person skilled in the art.
• the integral foams are preferably produced by the one-shot process with the help of low pressure or high pressure technology in closed, suitably temperature-controlled molding tools.
• the molds are usually made of metal, e.g. Aluminum or steel. These procedures are described, for example, by Piechota and Rschreib in "Integral Foam, Carl-Hanser-Verlag, Kunststoff, Vienna, 1975, or in the Kunststoff-Handbuch, Volume 7, Polyurethane, 3rd Edition, 1993, Chapter 7.
• auxiliaries and / or additives can also be added to the reaction mixture for producing the hybrid materials according to the invention.
• auxiliaries and / or additives can also be added to the reaction mixture for producing the hybrid materials according to the invention.
• examples include surface-active substances, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, hydrolysis protection agents, odor-absorbing substances and fungistatic and bacteriostatic substances.
• emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids, and salts of fatty acids with amines, e.g. oleic acid diethylamine, stearic acid diethanolamine, ricinoleic acid diethanolamine, salts of sulfonic acids, e.g. Alkali or ammonium salts of dodecylbenzene or
• Foam stabilizers such as siloxane Oxalkylene 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 residues are also suitable for improving the emulsifying action, the cell structure and / or stabilizing the foam
• Suitable release agents include: reaction products of fatty acid esters with polyisocyanates, salts from amino groups-containing polysiloxanes and fatty acids, salts from saturated or unsaturated (cyclo) aliphatic carboxylic acids with at least 8 carbon atoms and tertiary amines, and in particular internal release agents such as carboxylic acid esters and / or -amides produced by esterification or amidation of a mixture
• Fillers in particular reinforcing fillers, are understood to be the conventional 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 layered silicates such as antigorite, bentonite, serpentine, tinsel, amphibole, chrisotile, talc
• Metal oxides such as kaolin, aluminum oxides, titanium oxides, zinc oxide and iron oxides, metal salts such as chalk, heavy spar and inorganic pigments such as
• Kaolin china clay
• aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and natural and synthetic fibrous minerals such as wollastonite, metal and in particular glass fibers of various lengths, which can optionally be sized, are preferably used.
• suitable organic fillers are: carbon black, melamine, rosin,
• Cyclopentadienyl resins and graft polymers as well as cellulose fibers, polyamide, polyacrylonitrile, polyurethane, 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 granulate is preferably 20 volume percent and more, particularly preferably 50
• volume percent and more preferably 80 volume percent and more and in particular 90 volume percent and more, each based on the volume of the invention
• hybrid materials according to the invention in particular hybrid materials with a matrix of cellular polyurethane, are distinguished by very good adhesion of the matrix material to the foamed granules according to the invention. This breaks an inventive
• Hybrid material preferably not at the interface between matrix material and foamed granulate. This makes it possible to produce hybrid materials that are opposite
• conventional polymer materials especially conventional polyurethane materials with the same density have improved mechanical properties, such as tear resistance and elasticity.
• 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 elasticities with low density.
• the hybrid materials according to the invention in particular those based on integral foams, show high rebound elasticities with low density.
• Integral foams based on hybrid materials according to the invention are therefore outstandingly suitable as materials for shoe soles. This gives light and comfortable soles with good durability properties. Such materials are particularly considered
• hybrid materials according to the invention with a cellular matrix are, for example, suitable for upholstery, for example of furniture, and mattresses.
• Hybrid materials with a matrix made of a viscoelastic gel are particularly 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 for example used as floor coverings
• the properties of the hybrid materials according to the invention can depend on
• Polymer (PM) used vary widely and can be varied within wide limits in particular by varying the size, shape and nature of the expanded granulate, or by adding other additives, for example also other non-foamed granules such as plastic granules, for example rubber granules .
• hybrid materials according to the invention have a high durability and resilience, which is particularly noticeable through high tensile strength and elongation at break.
• hybrid materials according to the invention have a low density.
• Object / method / uses can be used not only in the respectively specified combination, but also in other combinations without leaving the scope of the invention.
• So z. B. also implicitly includes the combination of a preferred feature with a particularly preferred feature, or a feature that is not further characterized with a particularly preferred feature, etc., even if this combination is not expressly mentioned.
• Foamed granules comprising a thermoplastic polyurethane obtainable or obtained by reacting at least components (i) to (iii):
• a polyol composition (PZ) the isocyanate composition containing at least one aliphatic diisocyanate with a number average molecular weight less than 200 g / mol.
• Diisocyanate is flexamethylene diisocyanate (HDI).
• Chain extender (KV1) is selected from the group consisting of 1, 3-propanediol, 1, 2-ethanediol, 1, 4-butanediol, 1, 6-flexanediol and FIQEE.
• Polyol composition a polyol selected from the group consisting of
• Polyol composition a polyol selected from the group consisting of
• a method for producing a foamed granulate comprising the steps
• composition (Z1) comprising a thermoplastic polyurethane, the thermoplastic polyurethane being obtained or obtainable. Reaction of at least components (a) to (c):
• HDI Hexamethylene diisocyanate
• chain extender (KV1) is selected from the group consisting of 1,3-propanediol, 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol and HQEE.
• Polyol composition a polyol selected from the group consisting of
• Polyol composition a polyol selected from the group consisting of
• Shoe sole part of a shoe sole, a bicycle saddle, an upholstery, a mattress, pad, handle, protective film, a component in the automotive interior and exterior.
• thermoplastic polyurethane is thermoplastic polyurethane.
• Polyurethane foam is.
• Polyol 1 polyether polyol with an OH number of 1 12.2 and exclusively primary
• chain extender 1 1, 4-butanediol
• Isocyanate 1 aliphatic isocyanate (1, 6-hexamethylene diisocyanate)
• Isocyanate 2 aromatic isocyanate (4,4'-methylene diphenyl isocyanate)
• Catalyst 1 tin-Il-dioctoate (50% in DOA)
• Catalyst 2 tin-Il-dioctoate (10% in DOA)
• Antioxidant 1 sterically hindered phenol
• Antioxidant 2 sterically hindered phenol
• TPU crosslinker 1 Thermoplastic polyurethane with an NCO content of 8.5% and a functionality of 2.05 by adding oligomeric MDI
• the examples TPU 1 to 4 listed below were produced in a twin-screw extruder, ZSK58 MC, from Coperion with a process length of 48D (12 housings).
• the melt was discharged from the extruder using a gear pump. After melt filtration, the polymer melt was processed into granules by means of underwater granulation, which were continuously dried in a heating fluidized bed at 40-90 ° C.
• the polyol, the chain extender and the diisocyanate and possibly a catalyst were metered into the first zone. Additional additives, as described above, are fed in zone 8.
• the housing temperatures are in the range of 150 - 230 ° C.
• the melt is discharged and underwater pelletized at melt temperatures of 210 - 230 ° C.
• the screw speed is between 180 and 240 1 / min.
• the throughput is in the range of 180 - 220 kg / h.
• thermoplastic polyurethanes (Table 1), a twin-screw extruder with a screw diameter of 44 mm and a length to diameter ratio of 42 with a subsequent melt pump, a start-up valve with screen changer, a perforated plate and an underwater pelletizer.
• the thermoplastic polyurethane was dried at 80 ° C. for 3 h before processing in order to obtain a residual moisture content of less than 0.02% by weight.
• a TPU was added to which 4,4'-diphenylmethane diisocyanate with an average functionality of 2.05 was added in a separate extrusion process.
• thermoplastic polyurethane used in each case and the TPU crosslinker 1 were each metered separately into the feed of the twin-screw extruder via gravimetric metering devices.
• the materials After the materials had been metered into the feed of the twin-screw extruder, they were melted and mixed. The blowing agents C02 and N2 were then added via an injector. The remaining extruder length was used for the homogeneous incorporation of the blowing agents into the polymer melt.
• the polymer / blowing agent mixture was pressed into a perforated plate (LP) by means of a gear pump (ZRP) via a start-up valve with a screen changer (AV), separated into strands in the perforated plate into strands which were flowed through with a tempered liquid and under pressure in the cutting chamber the underwater pelletizer (UWG) cut into pellets and transported away with the water and thereby expanded.
• LP perforated plate
• ZRP gear pump
• AV screen changer
• the separation of the expanded particles from the process water is ensured by means of a centrifugal dryer.
• the total throughput of the extruder, polymers and blowing agent was 40 kg / h.
• the amounts of the polymers used and of the blowing agents are listed in Table 2.
• the polymers always form 100 parts while the blowing agents are also counted, so that total compositions above 100 parts are obtained.
• the expanded granules 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 in order to remove the remaining surface water and any moisture present in the particles and not to falsify further analysis of the particles.
• Impregnation kettle manufactured.
• the vessel was filled with a solid / liquid phase with a filling level of 80%, the phase ratio being 0.32.
• the solid phase is the TPU1 or TPU2 and the liquid phase is the mixture of water with calcium carbonate and a surface-active substance.
• the blowing agent butane
• the blowing agent was injected onto this mixture in the gas-tight vessel, which had previously been flushed with nitrogen, in the amount given in Table 5, based on the solid phase (TPU1 or TPU 2).
• the kettle was stirred while the
• Solid / liquid phase heated and at a temperature of 50 ° C defined nitrogen pressed up to a pressure of 8 bar. Then it was up to the desired
• Impregnation temperature heated further.
• the boiler was released via a valve after a given holding time. The exact manufacturing parameters of the tests as well as the achieved
• TPU3 and TPU4 were foamed, which have a hard phase made of MDI but have the same Shore hardness as the TPU 1 or TPU 2, also in the impregnation process as described above.
• the vessel was filled with a solid / liquid phase with a filling level of 80%, the phase ratio being 0.32.
• the solid phase is the TPU3 or TPU4 and the liquid phase is the mixture of water with calcium carbonate and a surface-active substance.
• the blowing agent butane
• the kettle was stirred while the
• Solid / liquid phase heated and at a temperature of 50 ° C defined nitrogen pressed up to a pressure of 8 bar. Then it was up to the desired
• Impregnation temperature (IMT) heated further.
• IMT Impregnation temperature
• Measurement methods For material characterization, the following measurement methods can be used:

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