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
  • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
• • A—HUMAN NECESSITIES
  • A43—FOOTWEAR
  • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
  • A43B13/00—Soles; Sole-and-heel integral units
  • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
  • A43B13/04—Plastics, rubber or vulcanised fibre
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
  • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
• • 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
  • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/24—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by surface fusion and bonding of particles to form voids, e.g. sintering
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C2948/00—Indexing scheme relating to extrusion moulding
  • B29C2948/92—Measuring, controlling or regulating
  • B29C2948/92504—Controlled parameter
  • B29C2948/92704—Temperature
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/48—Wearing apparel
  • B29L2031/50—Footwear, e.g. shoes or parts thereof
  • B29L2031/504—Soles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/48—Wearing apparel
  • B29L2031/50—Footwear, e.g. shoes or parts thereof
  • B29L2031/507—Insoles
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/0066—≥ 150kg/m3
• • 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
  • C08G2350/00—Acoustic or vibration damping material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • 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
  • 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
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/22—Thermoplastic resins
• • 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
  • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2425/02—Homopolymers or copolymers of hydrocarbons
  • C08J2425/04—Homopolymers or copolymers of styrene
  • C08J2425/06—Polystyrene

Definitions

• Particle foams or particle foams, particle foam
• shaped articles based thereon on the basis of thermoplastic polyurethane or other elastomers are known (for example WO 94/20568, WO 2007/082838 A1, WO2017030835, WO 2013/153190 A1
• Particle foam or particle foam in the sense of the present invention denotes a foam in the form of a particle, wherein the average diameter of the particle foam is between 0.2 to 20, preferably 0.5 to 15 and in particular between 1 to 12 mm.
• non-spherical, e.g. elongated or cylindrical particle foam is meant by diameter the longest dimension.
• Sufficient bonding or welding of the particle foams is essential in order to obtain advantageous mechanical properties of the molded part produced from the particle foam.
• its properties can not be used to their full extent, as a result of which the overall mechanical properties of the molded part obtained are adversely affected.
• the mechanical properties at the weakened sites are unfavorable with the same result as mentioned above.
• the application which is of primary importance for the subject of the present invention is the use in the shoe sector, wherein the particle foams can be used for shaped bodies for components of the shoe in which cushioning and / or padding is relevant, such as e.g. Midsoles and inserts.
• a shaped particle of foam with low compression properties fundamentally a higher density and thus more material than a molded body of foam particles with high compression properties in order to genrieren at the end similar properties.
• the applicability of a particle foam for specific applications is also given by this connection.
• particle foams are advantageous in which the compression properties of the molded articles produced from the particle foams are rather low with little force, and in the region in which the shoe is worn have a deformation which is sufficient for the wearer.
• a further problem is that in the case of large-scale production of particle foam via extrusion, the highest possible throughput of material is desirable in order to produce the required quantities in as short a time as possible.
• too fast processing of the material into inferior material leads to instability and / or collapse of the obtained particle foams. Accordingly, there is still a need to provide particle foams in which the production time is as low as possible.
• thermoplastic polyurethane as component I
• the shaped body is a midsole for shoes, is an insert for shoes or is a padding element for shoes.
• thermoplastic polyurethanes used as component I are well known.
• the preparation is carried out by reacting (a) isocyanates with (b) isocyanate-reactive compounds, for example polyols, having a number average molecular weight of 500 g / mol to 100,000 g / mol (b1) and optionally chain extenders having a molecular weight of 50 g / mol to 499 g / mol (b2), if appropriate in the presence of (c) catalysts and / or (d) customary auxiliaries and / or additives.
• isocyanates for example polyols, having a number average molecular weight of 500 g / mol to 100,000 g / mol (b1) and optionally chain extenders having a molecular weight of 50 g / mol to 499 g / mol (b2)
• thermoplastic polyurethanes are obtainable by reacting (a) isocyanates with (b) compounds which are reactive toward isocyanates, for example polyols (b1) having a number-average molecular weight of from 500 g / mol to 100 000 g / mol and one Chain extender (b2) having a molecular weight of 50 g / mol to 499 g / mol, if appropriate in the presence of (c) catalysts and / or (d) customary auxiliaries and / or additives.
• the components (a) isocyanate, (b) isocyanate-reactive compounds, for example polyol (b1), and optionally chain extenders (b2) are mentioned individually or together as synthesis components.
• the synthesis components including the catalyst and / or the customary auxiliaries and / or additives are also called feedstocks.
• the amounts used of the synthesis components (b) can be varied in their molar ratios, the hardness and the melt viscosity increasing with increasing content of chain extender in the component (b), while Melt index decreases with a constant molecular weight of the TPU.
• thermoplastic polyurethanes To prepare the thermoplastic polyurethanes, the synthesis components (a), (b), where (b) in a preferred embodiment also contains chain extenders, in the presence of a catalyst (c) and optionally auxiliaries and / or additives in such quantities Reaction that the equivalence ratio of NCO groups of the diisocyanates (a) to the sum of the hydroxyl groups of component (b) in the range of 1 to 0.8 to 1 to 1.3.
• the index is defined by the ratio of the total of the isocyanate groups used in the reaction to the isocyanate-reactive groups, ie in particular the reactive groups of the polyol component and the chain extender. With a figure of 1000, an isocyanate group has an active hydrogen atom. For ratios above 1000, more isocyanate groups exist than isocyanate-reactive groups.
• the ratio in the reaction of the abovementioned components is in the range from 965 to 1110, preferably in the range from 970 to 110, more preferably in the range from 980 to 1030 and very particularly preferably in the range from 985 to 1010 particularly preferred.
• thermoplastic polyurethanes are preferably prepared in which the thermoplastic polyurethane has a weight-average molecular weight (M w ) of at least 60,000 g / mol, preferably of at least 80,000 g / mol and in particular greater than 100,000 g / mol.
• M w weight-average molecular weight
• the upper limit for the weight-average molecular weight of the thermoplastic polyurethanes is generally determined by the processability as well as the desired property spectrum.
• the number-average molecular weight of the ther- thermoplastic polyurethanes between 80,000 and 300,000 g / mol.
• the average molecular weights stated above for the thermoplastic polyurethane as well as for the synthesis components (a) and (b) are the weight average determined by means of gel permeation chromatography (eg according to DIN 55672-1, March 2016 or analogous).
• organic isocyanates (a) it is possible to use aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates.
• the aliphatic diisocyanates used are customary aliphatic and / or cycloaliphatic 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-cyclohe
• Suitable aromatic diisocyanates are, in particular, 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), S'-dimethyl ⁇ '- diisocyanato-diphenyl (TODI), p-phenylene diisocyanate (PDI ), Diphenylethane-4,4'-diisoyanate (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-na
• mixtures can also be used.
• examples of mixtures are mixtures which contain, in addition to 4,4'-methylene diphenyl diisocyanate and at least one further methylene diphenyl diisocyanate.
• methylene diphenyl diisocyanate denotes 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate or a mixture of two or three isomers.
• the polyisocyanate composition may also contain further, the above-mentioned polyisocyanates.
• mixtures are containing polyisocyanate compositions
• the polyisocyanate composition contains 4,4'-MDI in an amount of 2 to 50% based on the total polyisocyanate composition and the other isocyanate in an amount of 3 to 20% based on the total polyisocyanate composition.
• crosslinkers for example the above-mentioned higher-functional polyisocyanates or polyols, or also other higher-functional molecules having a plurality of isocyanate-reactive functional groups. It is likewise possible within the scope of the present invention to achieve cross-linking of the products by an excess of the isocyanate groups used in relation to the hydroxyl groups.
• isocyanates examples include triisocyanates, e.g. B. triphenylmethane-4,4 ', 4 "-triisocyant and isocyanurates, furthermore the cyanurates of the aforementioned diisocyanates, as well as the oligomers obtainable by partial reaction of diisocyanates with water, eg the biurets of the aforementioned diisocyanates, furthermore oligomers obtained by targeted implementation of semiblocked diisocyanates with polyols having an average of more than two and preferably three or more hydroxy groups are available.
• the polyisocyanate composition may also contain one or more solvents.
• Suitable solvents are known to the person skilled in the art. Suitable examples are non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons.
• Preferred isocyanate-reactive compounds (b1) are those having a molecular weight between 500 g / mol and 8000 g / mol, more preferably 500 g / mol to 5000 g / mol, in particular 500 g / mol to 3000 g / mol.
• the isocyanate-reactive compound (b) has on statistical average at least 1, 8 and at most 2.2, preferably 2, Zerewitinow active hydrogen atoms, this number is also referred to as functionality of the isocyanate-reactive compound (b) and gives the amount of a substance theoretically reduced to a molecule amount of the isocyanate-reactive groups of the molecule.
• the isocyanate-reactive compound is preferably substantially linear and is an isocyanate-reactive substance or a mixture of various substances, in which case the mixture satisfies the said requirement.
• the ratio of components (b1) and (b2) is varied so as to obtain the desired hard segment content, which can be calculated according to the formula disclosed in PCT / EP2017 / 079049.
• a Hartsegementanteil is less than 60%, preferably less than 40%, more preferably less than 25% suitable.
• the isocyanate-reactive compound (b1) preferably has a reactive group selected from the hydroxyl group, the amino group, the mercapto group or the carboxylic acid. acid group. It is preferably the hydroxyl group and very particularly preferably primary hydroxyl groups.
• the isocyanate-reactive compound (b) is particularly preferably selected from the group of the polyester oil, the polyether oil or the polycarbonate diols, which are also combined under the term "polyols".
• homopolymers such as, for example, polyether oxide are suitable, polyester oxide, polycarbonate (diol) s, polysiloxane diols, polybutadiene diols, but also block copolymers and hybrid polyols, such as e.g. Poly (ester / amide).
• preferred polyetheroils are polyethylene glycols, polypropylene glycols, polytetramethylene glycol (PTHF), polytrimethylene glycol.
• Preferred polyester polyols are polyadipates, polysuccinic acid esters and polycaprolactones.
• the present invention also relates to a thermoplastic polyurethane as described above, wherein the polyol composition 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 ethers and ester blocks, for example polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or polyethers with polycaprolactone end blocks.
• Polyetheroic preferred are polyethyleneglycols according to the invention, polypropylene glycols, polytetramethylene glycol (PTHF) and Polytri methylenglykol. Further preferred is polycaprolactone.
• the polyol used has a molecular weight Mn in the range from 500 g / mol to 4000 g / mol, preferably in the range from 500 g / mol to 3000 g / mol.
• the present invention relates to a thermoplastic polyurethane as described above, wherein at least one polyol contained in the polyol composition has a molecular weight Mn in the range of 500 g / mol to 4000 g / mol.
• At least one polyol composition containing at least polytetrahydrofuran is used to prepare the thermoplastic polyurethane.
• the polyol composition in addition to polytetrahydrofuran also contain other polyols.
• polyethers are suitable as further polyols, for example, but also polyesters, block copolymers and hybrid polyols such as poly (ester / amide).
• Suitable block copolymers are, for example, those which have ethers and ester blocks, for example polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or also polyethers with Polycaprolactonendblöcken.
• Preferred polyetheroie are according to the invention polyethylene eneglycols, polypropylene glycols. Further preferred polycaprolactone is another polyol.
• Suitable polyols are, for example, polyethers, such as polytrimethylene oxide or polytetramethylene oxide.
• the present invention according to another embodiment relates to a thermoplastic polyurethane as described above, wherein the polyol composition at least one polytetrahydrofuran and at least one further polyol selected from the group consisting of a further polytetramethylene oxide (PTHF), polyethylene glycol, polypropylene glycol and Contains polycaprolactone.
• PTHF polytetramethylene oxide
• the polytetrahydrofuran has a number average molecular weight Mn in the range of 500 g / mol to 5000 g / mol, more preferably in the range of 550 to 2500 g / mol, particularly preferably in the range of 650 to 2000 g / mol and most preferably in the range of 650 to 1400 g / mol.
• the composition of the polyol composition can vary widely within the scope of the present invention.
• the content of the first polyol, preferably polytetrahydrofuran can be in the range of 15% to 85%, preferably in the range of 20% to 80%, more preferably in the range of 25% to 75%.
• the polyol composition may 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, 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 of 500 to 1400 g / mol.
• the number-average molecular weight Mn can be determined via gel permeation chromatography as mentioned above.
• the present invention also relates to a thermoplastic polyurethane as described above, wherein the polyol composition selected from the group consisting of polytetrahydrofurans having a number average molecular weight Mn in the range of 500 g / mol to 5000 g / contains mol.
• chain extenders (b2) are preferably aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 g / mol to 499 g / mol, preferably with 2 isocyanate-reactive compounds, which are also referred to as functional groups.
• Preferred chain extenders are diamines and / or alkanediols, more preferably alkanediols having 2 to 10 carbon atoms, preferably having 3 to 8 carbon atoms in the alkylene radical, which more preferably have only primary hydroxyl groups.
• chain extenders (c) are used, these are preferably aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 g / mol to 499 g / mol, preferably with 2 isocyanate-reactive groups, which are also functional groups be designated.
• the chain extender is at least one chain extender selected from the group consisting of 1, 2-ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2,3-butanediol, 1, 5-pentanediol, 1 , 6-hexanediol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanediol, 1, 4-dimethanolcyclohexane, neopentyl glycol and hydroquinone bis (beta-hydroxyethyl) ether (HQEE).
• chain extenders selected from the group consisting of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol and 1, 6-hexanediol and mixtures of the above-mentioned chain extenders.
• Examples of specific chain extenders and mixtures are disclosed inter alia in PCT / EP2017 / 079049
• catalysts (c) are used with the synthesis components. These are in particular catalysts which accelerate the reaction between the NCO groups of the isocyanates (a) and the hydroxyl groups of the isocyanate-reactive compound (b) and, when used, the chain extender.
• 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 tin organyl 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 the carboxylic acids such as Tin isooctoate, tin dioctoate, titanic acid ester or bismuth (III) neodecanoate.
• organyls such as tin organyl compounds, preferably tin dialkyls such as di
• catalysts are tin dioctoate, bismuth decanoate and titanic acid esters.
• the catalyst (d) is preferably used in amounts of from 0.0001 to 0.1 parts by weight per 100 parts by weight of the isocyanate-reactive compound (b).
• conventional auxiliaries (d) can also be added to the synthesis components (a) to (b). Mention may be made, for example, of surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricants and mold release agents, dyes and pigments, optionally stabilizers, preferably against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and / or plasticizer.
• Stabilizers in the context of the present invention are additives which protect a plastic or a plastic mixture against harmful environmental influences. Examples include primary and secondary antioxidants, hindered phenols, hindered amine light stabilizers, UV absorbers, hydrolysis inhibitors, quenchers and flame retardants. Examples of commercial stabilizers are given in Plastics Additives Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001 ([1]), p.98-S136.
• thermoplastic polyurethanes can be carried out according to the known methods dis- continuously or continuously, for example with reaction extruders or the tape method according to the "one-shot” - or the prepolymer process, preferably by the "one-shot” - method.
• the components (a), (b) reacting, in preferred embodiments, also the chain extender in component (b), (c) and / or (d) successively or simultaneously mixed together the polymerization reaction starts immediately.
• the TPU can then be directly granulated or convoluted by extrusion into lens granules. In this step, it is possible to include further additives or other polymers.
• the synthesis components (a), (b) and, in preferred embodiments, also (c), (d) and / or (e) are introduced into the extruder individually or as a mixture and, preferably, at temperatures of from 100.degree 280 ° C, preferably 140 ° C to 250 ° C, reacted.
• the resulting polyurethane is extruded, cooled and granulated or granulated directly via an underwater granulation as lens granules.
• thermoplastic polyurethane is prepared in a first step from the synthesis components isocanate (a), isocyanate-reactive compound (b) including chain extenders and in preferred embodiments the other starting materials (c) and / or (d) and in a second Extrusion step incorporated the additives or auxiliaries.
• a twin-screw extruder is used, since the twin-screw extruder works positively conveying and so a more precise adjustment of the temperature and discharge rate is possible on the extruder.
• the production and expansion of a TPU can be carried out in a reaction extruder in one step or via a tandem extruder according to methods known to the person skilled in the art.
• the styrene polymers mentioned as component II are standard polystyrene.
• the term "standard polystyrene” preferably comprises atactic, syndiotactic or isotactic polystyrene, particularly preferably atactic polystyrene.
• Atactic polystyrene according to the invention which is amorphous, has a glass transition temperature in the range of 100 ° C. ⁇ 20 ° C. (determined in accordance with DIN EN ISO 1 1357-1, February 2017 / DIN EN ISO 11357-2, July 2014, inflection point method) on.
• Syndiotactic and isotactic polystyrene according to the invention are each partially crystalline and have a melting point in the Range of respectively 270 ° C and 240 ° C (DIN EN ISO 11357-1, February 2017 / DIN EN ISO 11357-3, April 2013, W peak melting temperature).
• the polystyrenes used have a modulus of elasticity at tensile in excess of 2,500 (DIN EN ISO 527-1 / 2, June 2012).
• PS 158 K BASF SE
• PS 148 HQ BASF SE
• STYROLUTION PS 156 F STYROLUTION PS 158N / L
• STYROUTION PS 168N / L STYROLUTION PS 153F
• SABIC PS 125 SABIC PS 155
• SABIC PS 160 commercially available materials may also be used, e.g. PS 158 K (BASF SE), PS 148 HQ (BASF SE), STYROLUTION PS 156 F, STYROLUTION PS 158N / L, STYROUTION PS 168N / L, STYROLUTION PS 153F, SABIC PS 125, SABIC PS 155, SABIC PS 160 ,
• PS 158 K BASF SE
• PS 148 HQ BASF SE
• STYROLUTION PS 156 F STYROLUTION PS 158N / L
• STYROUTION PS 168N / L STYROLUTION PS 153F
• composition comprises Z
• thermoplastic polyurethane as component I
• the composition comprises Z
• thermoplastic polyurethane 80-90% by weight of thermoplastic polyurethane as component I
• composition Z may comprise, for example, 5 to 20% by weight of the styrene polymer as components II or from 5 to 15% by weight of the styrene polymer as components II.
• the composition Z may comprise, for example, 80 to 92.5% by weight of thermoplastic polyurethane as component I and 7.5 to 20% by weight of the styrene polymer as components II, preferably 80-90% by weight of thermoplastic polyurethane as component I and 10 to 20% by weight of the styrene polymer as components II, more preferably 80-85% by weight of thermoplastic polyurethane as component I and 15 to 20% by weight of the styrene polymer as components II, wherein the sum of the components I and II results in each case to 100% by weight.
• the non-expanded starting material, the composition Z, required for the production of the particle foam is prepared 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 unexpanded polymer mixture of composition Z required for the preparation of the particle foam is prepared in a known manner from the individual components and, if appropriate, other components such as processing aids, stabilizers, compatibilizers or pigments. Suitable processes are, for example, customary mixing processes with the aid of a kneader, continuous or discontinuous, or an extruder, such as a co-rotating twin-screw extruder.
• compatibilizers or auxiliaries such as stabilizers
• these can also be incorporated in the preparation of the components in this already.
• the individual components are combined before the mixing process or metered into the apparatus which takes over the mixing.
• the components are all dosed into the feeder and conveyed together into the extruder or individual components added via a side dosing (usually not for foams as this part of the extruder is not tight).
• 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 further of the abovementioned customary auxiliaries (d) are not melted, but incorporated in the solid state.
• the particle foams according to the invention generally have a bulk density of from 50 g / l to 200 g / l, preferably from 60 g / l to 180 g / l, particularly preferably from 80 g / l to 150 g / l.
• the bulk density is measured analogously to DIN ISO 697, whereby a vessel with 10 l volume is used instead of a vessel with 0.5 l volume in the determination of the above values, in contrast to the standard, since especially for the foam particles with lower Dense and large mass a measurement with only 0.5 l volume is too inaccurate.
• the diameter of the particle foams is between 0.5 to 30; preferably 1 to 15 and especially between 3 to 12 mm.
• diameter the longest dimension:
• the production of the particle foams can be carried out by the usual methods known in the prior art i. Providing a composition (Z) according to the invention.
• 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 the composition (Z) used.
• composition (Z) according to the invention in the form of a granule
• Another embodiment of the above method comprises a further step: i. Providing a composition (Z) according to the invention in the form of a granule;
• the granulate preferably has an average minimum diameter of 0.2-10 mm (determined via 3D evaluation of the granulate, for example via dynamic image analysis with the use of an optical measuring apparatus named 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 more preferably in the range from 7 to 32 mg.
• This average mass of the granules is determined as an arithmetic mean by weighing 3 times each of 10 granular particles.
• An embodiment of the abovementioned method comprises impregnating the granules with a propellant under pressure and subsequently expanding the granules in step (ii) and (iii):
• the impregnation in step ii) can be carried out in the presence in the presence of water and optional suspension aids 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 wt .-%, based on the composition of the invention.
• the impregnation temperatures are in the range of 100-200 ° C., depending on the selected pressure, the pressure in the reaction vessel being between 2 and 150 bar, preferably between 5 and 100 bar, particularly preferably between 20 and 60 bar, the duration of impregnation. generally takes 0.5 to 10 hours.
• Suitable propellants for carrying out the process in a suitable closed reaction vessel are e.g. organic liquids and gases which are in a gaseous state in the processing conditions, such as hydrocarbons or inorganic gases, or mixtures of organic liquids or gases and inorganic gases, which may 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 having 3 to 8 C 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 abovementioned gases.
• the impregnation of the granules with a blowing agent under pressure comprises processes and subsequent expansion of the granules in step (ii) and (iii):
• Suitable blowing agents in this process variant are volatile organic compounds having a boiling point at atmospheric pressure of 1013 mbar 35 from -25 to 150, in particular -10 to 125 ° C.
• Well suited are hydrocarbons (preferably halogen-free), in particular C4-10 alkanes, for example, the isomers of butane, pentane, hexane, heptane and octane, more preferably iso-pentane.
• Further possible blowing agents are also sterically more demanding compounds such as alcohols, ketones, esters, ethers and organic carbonates.
• the composition in step (ii) is melt-blended in an extruder with the blowing agent under pressure, which is fed to the extruder.
• the propellant-containing mixture is squeezed out under pressure, preferably with moderately controlled back pressure (for example, underwater granulation) and granulated.
• moderately controlled back pressure for example, underwater granulation
• the melt strand foams and granules give the particle foams.
• Suitable extruders are all conventional screw machines, in particular single-screw and twin-screw extruders (eg type ZSK from Werner & Pfleiderer), co-kneaders, Kombiplast machines, MPC kneading mixers, FCM mixers, KEX kneading screw extruders and shear roller extruders, as they eg in Saechtling (ed.), plastic paperback, 27th edition, Hanser-Verlag Kunststoff 1998, chap. 3.2.1 and 3.2.4 are described.
• 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 addition of the blowing agent of 40 to 200 bar, preferably 60 to 150 bar, more preferably 80 to 120 bar to ensure homogenization of the blowing agent with the melt.
• the implementation can be carried out in an extruder or an arrangement of one or more extruders.
• a first extruder the components can be melted and blended, and a propellant injected.
• the impregnated melt is homogenized and the temperature and / or the pressure are adjusted.
• the mixing of the components and the injection of the blowing agent can likewise be divided into two different process parts. If, as preferred, only one extruder is used, then all process steps, melting, mixing, injection of the blowing agent, homogenization and adjustment of the temperature and / or the pressure in an extruder are carried out.
• the corresponding, possibly even already colored, particle foam can be produced directly by impregnating the corresponding granulate with a supercritical fluid, from which the supercritical fluid is removed from
• 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 may also contain a polar fluid having a Hildebrand 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 dyed, foamed article is obtained.
• Another object of the present invention is a molded article produced from the particle foams according to the invention.
• the corresponding shaped bodies can be produced by methods known to the person skilled in the art.
• a preferred method for producing a foam molding comprises the following steps:
• step (ii) fusing the particle foams of step (i) according to the invention.
• the fusion in step (ii) is preferably carried out in a closed form, wherein the fusion can be effected by steam, hot air (as described for example in EP1979401 B1) or energetic radiation (microwaves or radio waves).
• the temperature at the fusing of the particle foam is preferably below or close to the melting temperature of the polymer from which the particle foam was made. Accordingly, the temperature for fusing the particle foam is between 100 ° C. and 180 ° C., preferably between 120 and 150 ° C., for the customary polymers.
• temperature profiles / residence 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, if appropriate in the presence of water or other polar liquids, such as e.g. polar group-containing microwave-absorbing hydrocarbons (such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols) and can be carried out in analogy to the processes described in EP3053732A or WO16146537.
• polar group-containing microwave-absorbing hydrocarbons such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols
• the particle foams can preferably be wetted with a polar liquid which is suitable for irradiating the radiation. absorb, for example, in proportions of 0.1 to 10 wt .-%, preferably in proportions of 1 to 6 wt .-%, based on the particle foams used.
• the welding with high-frequency electromagnetic radiation of the particle foams can also be achieved in the context of the present invention without the use of a polar liquid.
• the thermal bonding of the foam particles takes place, for example, in a mold by means of high-frequency electromagnetic radiation, in particular by means of microwaves.
• High-frequency is understood to mean electromagnetic radiation with frequencies of at least 20 MHz, for example of at least 100 MHz.
• electromagnetic radiation is used in the frequency range between 20 MHz and 300 GHz, for example between 100 MHz and 300 GHz.
• microwaves in the frequency range between 0.5 and 100 GHz, more preferably 0.8 to 10 GHz, and irradiation times of between 0.1 to 15 minutes.
• the frequency range of the microwave is adapted to the absorption behavior of the polar liquid or, conversely, the polar liquid is selected on the basis of the absorption behavior in accordance with the frequency range of the microwave device used. Suitable methods are described, for example, in WO 2016 / 146537A1.
• the particle foam may also contain dyes.
• the addition of dyes can take place via different routes.
• the produced particle foams can be colored after production.
• the corresponding particle foams are contacted 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 particle foam.
• TF carrier liquid
• Suitable dyes are, for example, inorganic or organic pigments.
• Suitable natural or synthetic inorganic pigments are, for example, 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 may be added in the production of the particle foam.
• the dye may be added to the extruder via extrusion.
• already dyed material can be used as the starting material for the production of the particle foam, which is extruded or expanded in a closed vessel according to the abovementioned methods.
• the supercritical fluid or the heated fluid may contain a dye.
• the molded parts according to the invention have advantageous properties for the abovementioned applications in the shoe or sports shoe sector.
• the tensile and compression properties of the moldings produced from the particle foams are characterized in that the tensile strength is above 600 kPa (DIN EN ISO 1798, April 2008), 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 standard is the height of the sample at 20 mm instead of 50 mm and thus the adaptation of the test speed to 2 mm / min).
• the rebound resilience of the moldings produced from the particle foams is above 55% (analogous to DIN 53512, April 2000, the deviation from the standard is the test piece height, which should be 12 mm, but in this test is carried out at 20 mm). beat "the sample and avoid measuring the ground).
• the density and compression properties of the molded bodies produced are related.
• the density of the molded parts produced is 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 particle foams of the invention is generally between 1, 5 and 2.5, preferably from 1.8 to 2.0.
• the invention further relates to the use of a particle foam according to the invention for the production of a molded article for shoe midsoles, shoe insoles, shoe combination soles.
• the particle foam according to the invention can be used for the production of a molding for bicycle saddles, bicycle tires, damping elements, upholstery, mattresses, underlays, handles, protective films, in components in the automotive interior and exterior, in balls and sports equipment or as a floor covering, in particular for sports surfaces. Athletics tracks, sports halls, children's playgrounds and sidewalks.
• a particle foam according to the invention for the production of a shaped body for shoe midsoles, shoe insoles, shoe combination soles or upholstery element for shoes.
• the shoe is preferably a street shoe, sports shoe, sandal, boots or safety shoe, particularly preferably a sports shoe.
• a further subject matter of the present invention is therefore also a molded article, wherein the molded article is a shoe combination sole for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
• Another object of the present invention is therefore also a molded article, wherein the molded article is a midsole for shoes, preferably for street shoes, sports shoes, sandal, boots or safety shoes, particularly preferably sports shoes.
• a further subject matter of the present invention is also a shaped body, wherein the shaped body is an insert for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
• a further subject matter of the present invention is also a shaped body, wherein the shaped body is a padding element for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
• the cushioning element may be e.g. Heel area or forefoot area can be used.
• a further subject of the present invention is therefore also a shoe in which the shaped article according to the invention is used as midsole, midsole or padding in the e.g. Heel area, forefoot area is used, wherein the shoe is preferably a street shoe, sports shoe, sandal, boots or safety shoe, particularly preferably a sports shoe.
• molded body made of particle foam comprising a composition (Z)
• thermoplastic polyurethane as component I
• the shaped body is a midsole for shoes, is an insole for shoes or is a padding element for shoes.
• thermoplastic polyurethane as component I.
• Shaped body according to embodiment 9 characterized in that the elongation at break is above 100%.
• Shaped body according to embodiment 9 or 10 characterized in that the
• a method for producing a shaped article according to one of the embodiments 1 to 17 comprising
• step (ii) fusing the particle foams from step (i).
• step (ii) takes place in a closed form.
• step (ii) by means of steam, hot air or energy radiation takes place.
• Shoe comprising a shaped body according to one of the embodiments 1 to 17.
• a particle foam having a composition according to one of Embodiments 1 to 3 for the production of a shaped article according to one of embodiments 1 to 17 for shoe midsoles, shoe insoles, shoe combination soles, pad elements for shoes, bicycle saddles, bicycle tires, damping elements, Upholstery, mattresses, underlays, handles, protective films, in automotive interior and exterior components, in balls and sports equipment, or as a floor covering.
• thermoplastic polyurethane For the preparation of the expanded particles of thermoplastic polyurethane and the styrene polymer, a twin-screw extruder with a screw diameter of 44 mm and a length to diameter ratio of 42 with subsequent melt pump, a start-up valve with screen changer, a perforated plate and an underwater pelletizer was used.
• the thermoplastic polyurethane was dried according to instructions before use at 80 ° C for 3 h to obtain a residual moisture content of less than 0.02 wt.%.
• it was likewise dried at 80 ° C. for 3 hours to a residual moisture content of less than 0.05% by weight.
• thermoplastic polyurethane 0.9% by weight, based on the thermoplastic polyurethane used, of a thermoplastic polyurethane was added to each test, which was mixed with 4,4'-diphenylmethane diisocyanate with an average functionality of 2.05 in a separate extrusion process , added.
• the thermoplastic polyurethane used was an ether-based TPU from BASF (Elastollan 1 180 A or Elastollan 1 185 A) having a Shore hardness of 80 A or 85 A according to the data sheet.
• the styrene polymer used was a PS 158 KQ from BASF with a modulus of elasticity measured in a tensile test of 3317 MPa according to the data sheet or a PS 148 H from BASF with a modulus of elasticity measured in the tensile test of 3300 MPa according to data sheet.
• thermoplastic polyurethane, the polystyrene and the thermoplastic polyurethane mixed with 4,4'-diphenylmethane diisocyanate were each metered separately via gravimetric metering devices into the intake of the twin-screw extruder.
• thermoplastic polyurethane Diphenylmethane diisocyanate added thermoplastic polyurethane, and the polystyrene are listed in Table 1.
• the melt mixture was then pressed by means of a gear pump (ZRP) via a start-up valve with screen changer (AV) into a perforated plate (LP) and cut into granules in the cutting chamber of underwater granulation (UWG) and with the tempered and pressurized water transported away and expanded.
• ZRP gear pump
• AV start-up valve with screen changer
• LP perforated plate
• UWG underwater granulation
• the separation of the expanded particles from the process water is ensured by means of a centrifugal dryer.
• Table 3 shows the amounts of blowing agent used (CO 2 and N 2 ) with the amounts each adjusted to give the lowest possible bulk density.
• the quantities of the blowing agents are based on the total throughput of polymer.

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• 2019
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