WO2022194664A1 - Particules de mousse fabriquées à partir d'un élastomère thermoplastique expansé et procédé de production - Google Patents

Particules de mousse fabriquées à partir d'un élastomère thermoplastique expansé et procédé de production Download PDF

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Publication number
WO2022194664A1
WO2022194664A1 PCT/EP2022/056172 EP2022056172W WO2022194664A1 WO 2022194664 A1 WO2022194664 A1 WO 2022194664A1 EP 2022056172 W EP2022056172 W EP 2022056172W WO 2022194664 A1 WO2022194664 A1 WO 2022194664A1
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WIPO (PCT)
Prior art keywords
wax
foam particles
granules
nonionic surfactant
thermoplastic elastomer
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PCT/EP2022/056172
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German (de)
English (en)
Inventor
Uwe Keppeler
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Basf Se
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Publication of WO2022194664A1 publication Critical patent/WO2022194664A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • 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
    • C08J9/14—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 organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J9/224—Surface treatment
    • 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
    • C08J2201/036—Use of an organic, non-polymeric compound to impregnate, bind or coat a foam, e.g. fatty acid ester
    • 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
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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

Definitions

  • Foam particles made from an expanded thermoplastic elastomer and method for their production
  • the invention relates to foam particles made from an expanded thermoplastic elastomer and a method for producing such particles.
  • Foam particles made of expanded thermoplastic elastomer can be used in many areas, for example in the production of molded parts such as load carriers, seat cushions, mattresses or soles for running shoes.
  • the foam particles are introduced into a tool, for example, and are subjected to steam or heated there, so that they fuse with one another on the outside.
  • the production of the moldings from the foam particles usually takes place at different locations than the production of the foam particles, it is necessary to transport them from the location of the manufacture of the foam particles to the location of the molding production.
  • the transport usually takes place in large containers, for example BigBags. These are filled and emptied via conveyors, with the material of the foam particles, their geometry and bulk density having a major impact on transport behavior. Even if the production of the foam particles and the production of the moldings take place in neighboring plants, transport, for example through pipelines, is necessary.
  • thermoplastic polyurethane TPU
  • a granulate is first produced from the thermoplastic polyurethane and this is then impregnated in a suspension under pressure and at a temperature above the softening point of the polymer with a blowing agent and expanded by relaxation to foam particles.
  • the blowing agent can also be added in an extruder and the foam particles are produced by expansion in underwater granulation.
  • suspension aids which generally contain a dispersant (release agent), usually an inorganic material, for example tricalcium phosphate, magnesium pyrophosphate, metal carbonate, kaolin and a surfactant, are added during the production of the foam particles in suspension. Since the dis If perforating agents often impede the subsequent processing into molded parts, this is usually removed from the foam particles, for which purpose washing with an acid, for example nitric acid, is carried out. In the case of nitrogen-containing thermoplastic elastomers (TPE) such as TPU, this often leads to yellowing of the resulting foam particles.
  • a dispersant release agent
  • an inorganic material for example tricalcium phosphate, magnesium pyrophosphate, metal carbonate, kaolin and a surfactant
  • EP-A 3 438 175 It is also known from EP-A 3 438 175 to apply a water-soluble anionic surfactant to the surface of the foam particles in order to improve the welding of the particles to form the molded part.
  • the object of the present invention was therefore to provide foam particles which can be processed into molded parts without the risk of blocking during transport and without additional washing steps.
  • a further object of the present invention is the provision of a method for preparing the foam particles.
  • the problem is solved by particles made of an expanded thermoplastic elastomer with a surface on which a nonionic surfactant or a wax is applied, the proportion of nonionic surfactant or wax being 0.05 to 1% by weight, based on the total mass of the particles.
  • the non-ionic surfactant or wax acts as an external lubricant that prevents the foam particles from sticking together so that they can be removed from BigBags and conveyed without blocking.
  • a further advantage of using a nonionic ten sids or wax as a lubricant is that this does not impede the subsequent processing of the foam material particles and in particular has no negative impact on the welding of the particles to the molded part and its physical, especially mechanical properties. Therefore, the surface coating should be washed off again without an additional washing step, but at the same time during further processing to form molded parts by welding with steam. It is therefore particularly advantageous if a water-soluble non-ionic surfactant or an easily washable wax is used.
  • the production of the foam particles from the thermoplastic elastomer with the nonionic surfactant or wax applied thereto is carried out according to the invention by a process comprising
  • the liquid in the pressure vessel contains a non-ionic surfactant or wax which accumulates on the surface of the granules during impregnation with the propellant
  • the granules contain 0.1 to 5% by weight of nonionic surfactant or wax, based on the total mass of the granules.
  • the nonionic surfactant or wax to the surface of the foam particles or granules in the apparatus in which the granules expand to form the foam particles as a result of relaxation of the blowing agent, since each time transport is carried out without any lubricant acting as a lubricant non-ionic surfactant or wax on the surface, blocking can already occur.
  • the apparatus in which the granulate is decompressed is, for example, a decompression kettle.
  • the foam particles are prepared according to the suspension process known to those skilled in the art, as described, for example, in WO-A 2007/082838 or WO-A 94/20568. ben is.
  • a granulate of the thermoplastic elastomer is introduced into a liquid, the suspension medium, in a pressure vessel.
  • suitable suspension mediums are water, polar organic solvents such as alcohols, ketones, or mixtures thereof.
  • the suspension aid serves in particular to ensure that the granulate particles do not agglomerate during impregnation with the propellant, but remain in the liquid as individual particles.
  • Ionic and nonionic surfactants are suitable as suspension aids.
  • the suspension auxiliaries are usually used in amounts of from 0.01 to 5% by weight.
  • the suspension thus obtained is heated until the liquid phase has a temperature within the softening range of the polymer.
  • the blowing agent is then introduced into the suspension, if appropriate under pressure.
  • Suitable blowing agents are, for example, halogenated hydrocarbons, saturated aliphatic hydrocarbons or inorganic gases, for example saturated hydrocarbons having 3 to 8 carbon atoms, nitrogen, air, ammonia, carbon dioxide or mixtures thereof.
  • the blowing agent is generally used in amounts of 1 to 50% by weight, based on the mass of the granules.
  • a nonionic surfactant is used as the suspension aid, this can also be the nonionic surfactant that is applied to the surface of the foam particles. If an ionic surfactant is used as the suspension medium, it is necessary to additionally apply a nonionic surfactant or a wax to the surface of the foam particles, which can be applied after impregnation or can also be included in the liquid.
  • the softening range is understood to mean the temperature range which lies between 50° C. below the melting point of the thermoplastic elastomer and at most the melting point of the thermoplastic elastomer, the melting point being determined by means of differential scanning calorimetry (DSC) according to ISO 11357- 3 (German version of April 1, 2013).
  • DSC differential scanning calorimetry
  • ISO 11357- 3 German version of April 1, 2013.
  • DSC is a thermoanalytical method that can be used to determine, for example, the glass temperature T G or the melting point T m during heating. When cooling from the melt, the onset of crystallization processes can be detected.
  • thermoplastic elastomers In the case of thermoplastic elastomers, several endothermic peaks can also be detected in the first heating cycle due to various phase transformations, depending on the composition of the TPE and the type and quantity of the additives and the thermal history. For this reason, the first heating (1st cycle) is usually run down to the melt, cooled again and the melting point during the second heating (2nd cycle) is determined as the maximum of the endothermic peak.
  • thermoplastic polyurethanes In the case of thermoplastic polyurethanes, the temperature history is standardized by heating the material to be tested at 100°C for 20 hours and then determining the melting point during the first heating. However, the endothermic peak is often very broad and flat.
  • the impregnation pressure depends, among other things, on the amount of blowing agent used and the impregnation temperature (IMT) used.
  • IMP and IMT are respectively the pressure and temperature at the end of the impregnation in step (b).
  • the impregnation of the granules in step (b) takes place at a pressure in the range 150 to 7500 kPa, more preferably in the range 200 to 5500 kPa and especially in the range 500 to 4000 kPa and expanding the granules to the foam particles in step (c) at the same pressure as in step (b).
  • the temperature at which the granules are impregnated in step (b) is preferably in a range between 30°C and the melting point of the granules, more preferably in a range between 50°C and the melting point of the granules and particularly in a range between 80°C and the melting point of the granules.
  • the softening point of the thermoplastic elastomer is the temperature determined according to DIN EN ISO 306, method A 50 (Vicat softening point).
  • the nonionic surfactant or wax is dissolved or dispersed in the liquid in the pressure vessel
  • the nonionic surfactant or wax is applied to the granules during impregnation with the propellant.
  • a uniform distribution of the non-ionic surfactant or wax on the surface of the granules results in particular from the fact that the granules are mixed with the propellant in the liquid during impregnation.
  • a mixing unit for example a stirrer, with which the liquid containing the granules is mixed in order to keep the granules in suspension in the liquid.
  • the propellant diffuses into the granulate.
  • the nonionic tenside or wax accumulates on the surface of the granules due to the molecular size and penetrates at most a small part into the granules. If a small proportion of the non-ionic surfactant or wax diffuses into the granules, this remains in the upper layers of the granules and thus after expansion in the upper layers of the foam particles.
  • this has the advantage that nonionic surfactant or wax does not reach the surface over a long period of time, possibly over the entire service life of a component that is made from the foam particles post-diffused.
  • the liquid in the pressure vessel is 0.1 to 5% by weight, preferably 0.1 to 3.0% by weight and in particular 0.2 to 2.0% by weight of nonionic surfactant or wax.
  • nonionic surfactant or wax used as a lubricant is contained in the liquid in which the granules are impregnated with the propellant, this particularly preferably also acts as a suspension aid.
  • This has the further advantage that, in addition to the nonionic surfactant or wax acting as a lubricant, which accumulates on the surface of the foam particles, no further suspension aid is required that can contaminate the foam particles and have to be removed from them before further processing.
  • nonionic surfactant or wax which is soluble in the liquid in which the granulate is impregnated with the propellant. Since water is particularly preferably used as the liquid for impregnating the granules with the propellant, a water-soluble nonionic surfactant is particularly preferably used. This then results in a homogeneous distribution of the nonionic surfactant in the Liquid so that the non-ionic surfactant settles evenly on the surface of the granules.
  • the nonionic surfactant or wax acting as a lubricant can also be applied to the foam particles after the granules have expanded.
  • the granules either in the form of a suspension or solution directly in the expansion tank or alternatively in an additional step after the production of the foam particles in solid form, the nonionic surfactant or wax being present in this case as a fine powder.
  • the application after the granules have expanded can take place either as an alternative or in addition to the application during impregnation with the blowing agent. Additional application is required when the amount of lubricant applied during impregnation with the propellant is insufficient.
  • the composition of the liquid with the nonionic surfactant or the wax particularly preferably corresponds to the composition of the liquid described above, in which the granules are in the first variant (i). impregnated with the propellant.
  • the amount of nonionic surfactant or wax on the surface of the foam particles or in total on the surface and as an internal slip additive inside the polymer matrix can be determined by a Soxhl et extraction. After 8 hours of extraction with hot toluene, the wax is detached from the granules. After subsequent complete removal of the non-polar solvent, the residue is dissolved in hot dimethylformamide. When this strongly polar solution cools down, only the slightly polar wax crystallizes out again and can be filtered off and quantified. In cases where the granules also contain internal slip additive, the detachment only has to be done from the surface of the foam particles by washing several times with cold toluene.
  • the nonionic surfactant or wax is applied dry in the form of a powder to the foam particles
  • the nonionic surfactant or wax and the foam particles are placed in a container which is then closed and then moved.
  • a container which is then closed and then moved.
  • the pulverulent nonionic surfactant or wax and the foam particles are intensively mixed with one another and the nonionic surfactant or wax is deposited on the surface of the foam particles.
  • the proportion of nonionic surfactant or wax to the total mass of the foam particles is in the range from 0.05 to 1.0% by weight, more preferably in the range from 0.05 to 0.5% by weight. and especially in the range of 0.1 to 0.25% by weight. This amount is enough to leave enough nonionic surfactant or wax on the surface to attach to the foam particles.
  • the individual grains of the nonionic surfactant or wax in powder form preferably have an average particle diameter dso in the range from 1 to 150 ⁇ m, more preferably in the range from 2 to 100 ⁇ m and in particular in the range from 2 to 50 ⁇ m
  • the application of the nonionic surfactant or wax to the foam particles in variant (ii) in powder form is preferably carried out at ambient pressure and ambient temperature.
  • the nonionic surfactant or wax is applied at elevated pressure or at elevated temperature.
  • the nonionic surfactant or wax is applied at a temperature below the softening point of the thermoplastic elastomer and the nonionic surfactant or wax used.
  • the application of the nonionic surfactant or wax is at ambient temperature.
  • the nonionic surfactant or wax can also be added to the thermoplastic elastomer as an additive in the range from 0.1 to 5% by weight (internal lubricant).
  • the nonionic surfactant or wax used as an additive migrates through the polymer material to its surface and is thus deposited on the surface of the foam particles produced.
  • 0.05 to 1 wt 0.1 to 5% by weight more preferably in the range from 0.1 to 3% by weight and in particular in the range from 0.5 to 2% by weight, based in each case on the total polymer mass.
  • the rate of migration of the internal lubricant depends on the polarity and crystallinity of the TPE as well as the structure and molecular weight of the internal lubricant.
  • the optimum concentration range of the additive must be matched to the polymer matrix of the granules and the internal lubricant must not be completely soluble in the polymer matrix of the granules.
  • Suitable waxes are, for example, partially synthetic waxes such as ester waxes or amide waxes and synthetic waxes such as polyolefin waxes, polyester waxes, polyethylene glycol waxes and PTFE waxes.
  • Amide waxes are particularly preferred, in particular selected from stearic acid amide, oleic acid amide, behenic acid amide and ethylenebisstearylamide. There can also be mixtures of two or more of these components or mixtures of nonionic surfactants and waxes are used.
  • thermoplastic elastomer which can be expanded to form foam particles and in which a granulate can be impregnated with a blowing agent by the method described above can be used as the thermoplastic elastomer.
  • thermoplastic elastomers are known per se to those skilled in the art. Suitable thermoplastic elastomers are described, for example, in “Handbook of Thermoplastic Elastomers", 2nd edition, June 2014.
  • the thermoplastic elastomer can be a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester, an olefin-based thermoplastic elastomer, a crosslinked olefin-based thermoplastic elastomer or a thermoplastic vulcanizate, or a thermoplastic styrene-butadiene block copolymer.
  • the thermoplastic elastomer is a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, or a polyesterester.
  • the thermoplastic elastomer is particularly preferably a thermoplastic polyurethane.
  • thermoplastic elastomers are used in step (a) in the form of granules.
  • the diameter means the longest dimension.
  • the individual granulate particles generally have an average mass in the range from 1 to 80 mg, preferably in the range from 3 to 60 mg and particularly preferably in the range from 4 to 45 mg.
  • This average mass of the granulate particles is determined as the arithmetic mean by weighing 10 granulate particles three times.
  • This preferably cylindrical or round granulate can be produced by any compounding process known to those skilled in the art, with subsequent granulation as a cold or diligent cut. For example, by compounding, optionally together with other additives in a twin-screw extruder, pressing out of the extruder, optionally cooling and granulating. Corresponding methods are described, for example, in Kunststoff Taschenbuch, Flanser-Verlag, 28th edition, 2001.
  • any other additives in the granules can be, for example, antioxidants, stabilizers, flame retardants, fillers, pigments and dyes, in addition to internal lubricants (nonionic surfactant or wax).
  • Nucleating agents such as talc, carbon black, graphite, pyrogenic silica, natural or synthetic zeolites or bentonites are preferably used to adjust the cell structure. These are generally used in amounts ranging from 0.01 to 5% by weight, based on the granules.
  • the pourability (flow behavior) of plastics in granular form is determined according to DIN EN ISO 6186 (1998-08). The pourability is determined by the different types of frictional resistance that overlap between the particles that are in contact.
  • the granules containing blowing agent obtained in step (b) can be foamed in a subsequent step (c) by decompression to give foam particles.
  • the suspension is generally expanded in step (c) by emptying the pressure vessel via an open shut-off valve into an expansion vessel.
  • a valve, a slider, a tap or a flap can be used as the shut-off valve; the shut-off valve is preferably a ball valve.
  • the suspension can be expanded directly to atmospheric pressure (1013 Pa) or into an intermediate vessel with an excess pressure in the range from 100 to 1000 kPa.
  • step (c) the suspension is brought into contact with a liquid coolant in step (c) after the expansion device.
  • This step also referred to as quenching, is described in EP-A 2 336225, for example, for the production of expandable polypropylene (EPP).
  • the suspension aids used and still adhering, the dispersant (release agent), must be removed from the foam particles obtained in a work-up step, for example by means of an acid wash.
  • the foam particles are then washed and separated from the liquid phase by filtration or centrifugation and then dried.
  • the surfactants used as suspension aids are usually also completely removed from the surface of the foam particles. This can be demonstrated by simple analytical methods (e.g. elementary analysis for sodium n-alkyl(Cio-Ci3)benzenesulfonate).
  • the foam particles are separated from the liquid phase in the expansion tank without an additional washing step and then dried.
  • the foam particles made of thermoplastic elastomers produced by the process according to the invention are predominantly closed-cell and have a cell density (number of cells/area) of 1 to 1500 cells/mm 2 and preferably a bulk density in the range of 20 to 250 kg/m 3 , particularly preferably in the range from 35 to 150 kg/m 3 .
  • thermoplastic elastomers in granular form 3 - 7 mg are heated in a first cycle from -80°C to 220°C at a heating rate of 20°C/min, then at 20°C/min to -80° C, followed by another heating cycle with a heating rate of 20°C/min.
  • the temperature of the endothermic peak maximum in the second heating cycle was given as the melting point.
  • thermoplastic polyurethanes the granules or injection-molded sheets produced from them are heated at 100° C. for 20 h and the melting point is determined in the first cycle.
  • the softening range is the temperature range in which thermoplastics can be permanently deformed. To describe this range, a softening point that is within this range can be specified.
  • the softening point of the thermoplastic elastomer is determined according to DIN EN ISO 306, method A 50 (Vicat softening point).
  • the average particle size is determined according to ISO 13320:2009 (particle size analysis - laser diffraction methods) and is given as the average particle diameter dso.
  • IMT is the temperature at the end of the impregnation in step (b) at which the stress relieving step (c) is initiated.
  • IMP is the pressure that has been established at the end of the impregnation in step (b) at the IMT and at which the relaxation step (c) is initiated.
  • the phase ratio P is defined as the ratio of granulate, measured in kilograms, to suspension medium, which is preferably water, also in kilograms.
  • the residence time (VZ) is defined as the time [min] during which the temperature of the liquid phase is in a temperature range of 5°C below the IMT and 2°C above the IMT.
  • the determination is based on DIN EN ISO 60 (January 2000).
  • the foam particles are filled into a measuring cylinder with a known volume using a funnel with a defined geometry (completely filled with bulk material), the excess bulk material is scraped off the measuring cylinder with a straight-edged rod and the content of the measuring cylinder is determined by weighing.
  • the funnel used is approx. 40 cm high, has an opening angle of 40° and an outlet with a diameter of 50 mm.
  • the measuring cylinder has an inner diameter of 188 mm and a volume of 10 l.
  • the foam particles to be tested are conditioned for 24 hours in standard climate according to ISO 291 (23+/-1° C., 50+/-5% relative humidity) and tested in the same climate.
  • the bulk density (SD) was calculated from the mass of the fill [kg]/0.01 [m 3 ].
  • the mean value from 3 measurements in kg/m 3 was given as the bulk density.
  • test devices are significantly larger.
  • a hopper according to the bulk density measurement is used, enclosing above the conical part of the hopper a cylindrical part with an inner diameter of 300 mm, so that the total capacity of the hopper is 40 liters.
  • the outlet nozzle has an inner diameter of 50 mm and a length of 50 mm.
  • the foam particles to be tested are conditioned for 24 hours in standard climate according to ISO 291 (23+/-1° C., 50+/-5% relative humidity) and tested in the same climate.
  • the outflow time t is the time that a defined mass or a defined volume of the sample needs to flow through the funnel with the specified dimensions. It is specified in seconds [s].
  • the funnel is filled and the bed is subjected to a surface load of 7 kg (1004 Pa) for 16 hours. The load is then relieved again and the outflow time t ge is measured.
  • a quantity of between 10 and 20 g, precisely determined using a precision balance, is extracted in an extraction apparatus with 100 ml of toluene for 8 hours.
  • the toluene in the storage vessel is then concentrated using a rotary evaporator and the residue in the storage vessel is dried at 80° C. in a suction-controlled heating cabinet.
  • the residue is then heated with 50 ml of N,N-dimethylformamide (DMF) until a clear solution is obtained.
  • the wax which has crystallized out at room temperature is separated off quantitatively using a glass filter crucible and dried at 80° C. in a heating cabinet to constant weight.
  • the amount precisely determined with a precision scale is stated in relation to the amount weighed in as a percentage.
  • the tensile strength is determined on panels with a target thickness of 10 mm (thickness can vary slightly depending on shrinkage) based on DIN EN ISO 1798 (04/01/2008). The required type 1 test specimens are punched out. The test panels used were conditioned beforehand for at least 16 hours in a standard climate (23 ⁇ 2 °C and 50 ⁇ 5% humidity). The tensile test is also carried out in this standard climate. The tensile strength a max (specified in kPa) is calculated using Equation (1), it is the maximum stress that can be identical to the stress at break.
  • thermoplastic elastomers used in the examples of the invention and the comparative examples are listed in Table 1.
  • additives contained in the granulate produced from this by compounding and the particle weights are also listed in Table 1.
  • TPU1 to TPU5 are aromatic thermoplastic polyether-polyurethane elastomers
  • TPU6 is an aliphatic thermoplastic polyether-polyurethane elastomer
  • the tests were carried out with a vessel filling level of 85% by volume and a phase ratio of 0.52.
  • the pressure is released via an expansion device into a pressureless stirred tank (expansion tank).
  • the gas space in the pressure vessel is set to a specified pressure and kept constant during the expansion.
  • the relaxation jet can optionally also be cooled with a specific volume flow of water at a specific temperature (water quench).
  • the foam particles are then separated directly from the liquid phase by filtration or centrifugation and then dried.
  • a dispersing agent e.g. tricalcium phosphate, based on the amount of granules is also added to the impregnation vessel. After depressurization in the expansion tank, this dispersing agent must be removed with an acid wash, with nitric acid and further wash steps with deionized water.
  • the bulk density (SD) of the resulting foam particles is measured and the pourability is determined.
  • the foam particles of the comparative examples generally tend to bond more easily. They therefore generally have to be sieved after drying, which leads to a loss in yield compared to the examples according to the invention.
  • the impregnation takes place as in variant (i).
  • the nonionic surfactant or wax is applied after decompression, either by adding a certain amount of deionized water with the appropriate amount of the nonionic surfactant or the wax to the expansion vessel, or by applying the nonionic surfactant or the wax as a dry powder to the dried foam particles .
  • the moldings were produced on a commercial EPP molding machine (type K68 from Kurtz GmbH).
  • thermoplastic elastomers of the comparative examples can only be produced from the thermoplastic elastomers of the comparative examples by using special filling processes, as described in EP-A 2,671,633.
  • 19 % by weight refers to the amount of granules used 1 tricalcium phosphate 1 sodium n-alkyl (CioCi3) benzene sulfonate 2 Lutensol AT25 (BASF SE) 1 ethylene bisstearylamide (added as a 34% aqueous suspension. The percentage by weight in the table refers to the solids content) Table 2b: Test parameters for Examples 1 to 12 and Comparative Examples 13 to 19

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Abstract

L'invention concerne des particules de mousse fabriquées à partir d'un élastomère thermoplastique expansé présentant une surface sur laquelle est appliqué un tensioactif non ionique ou une cire, la proportion de tensioactif non ionique ou de cire allant de 0,05 à 1 % en poids, par rapport à la masse totale des particules de mousse. L'invention concerne également un procédé permettant de produire les particules de mousse, dans lequel une matière granulaire est introduite dans un liquide dans un récipient sous pression, la matière granulaire est imprégnée avec un agent moussant à une température élevée et sous une pression élevée, et la matière granulaire est dépressurisée et la matière granulaire imprégnée avec l'agent moussant se dilate afin de former des particules de mousse, le liquide dans le récipient sous pression contenant un tensioactif non ionique ou une cire qui s'accumule sur la surface de la matière granulaire pendant l'imprégnation avec l'agent moussant, ou un tensioactif non ionique ou une cire est appliqué sur les particules de mousse fabriquées à partir d'un élastomère thermoplastique expansé après que la matière granulaire imprégnée avec l'agent moussant a été dépressurisée, et/ou la matière granulaire contient de 0,1 à 5 % en poids d'un tensioactif non ionique ou d'une cire, rapporté à la masse totale de la matière granulaire.
PCT/EP2022/056172 2021-03-15 2022-03-10 Particules de mousse fabriquées à partir d'un élastomère thermoplastique expansé et procédé de production WO2022194664A1 (fr)

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EP21162626 2021-03-15
EP21162626.2 2021-03-15

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WO2022194664A1 true WO2022194664A1 (fr) 2022-09-22

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020568A1 (fr) 1993-03-11 1994-09-15 Basf Aktiengesellschaft Mousses a base de polyurethannes thermoplastiques
US20030073752A1 (en) * 2001-09-28 2003-04-17 Ronald Gabbard Anti-lumping compounds for use with expandable polystyrene beads
WO2007082838A1 (fr) 2006-01-18 2007-07-26 Basf Se Mousse a base de polyurethane thermoplastique
EP2336225A1 (fr) 2009-12-17 2011-06-22 Basf Se Procédé de fabrication de particules en mousse de polyoléfine
EP2671633A1 (fr) 2012-06-06 2013-12-11 Basf Se Procédé de transport de particules de polymère thermoplastiques moussées
EP3438175A1 (fr) 2016-03-31 2019-02-06 JSP Corporation Particules de mousse de polyuréthane thermoplastique et procédé de fabrication d'un article moulé à partir de particules de mousse de polyuréthane thermoplastique
CN110003635A (zh) * 2019-03-29 2019-07-12 江南大学 一种发泡热塑性聚氨酯弹性体、制备方法和应用
US20190345284A1 (en) * 2016-11-14 2019-11-14 Basf Se Expanded thermoplastic polyurethane beads, production thereof and production of a molded part
EP3578068A1 (fr) * 2017-01-31 2019-12-11 ASICS Corporation Élément semelle et chaussure

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020568A1 (fr) 1993-03-11 1994-09-15 Basf Aktiengesellschaft Mousses a base de polyurethannes thermoplastiques
US20030073752A1 (en) * 2001-09-28 2003-04-17 Ronald Gabbard Anti-lumping compounds for use with expandable polystyrene beads
WO2007082838A1 (fr) 2006-01-18 2007-07-26 Basf Se Mousse a base de polyurethane thermoplastique
EP2336225A1 (fr) 2009-12-17 2011-06-22 Basf Se Procédé de fabrication de particules en mousse de polyoléfine
EP2671633A1 (fr) 2012-06-06 2013-12-11 Basf Se Procédé de transport de particules de polymère thermoplastiques moussées
EP3438175A1 (fr) 2016-03-31 2019-02-06 JSP Corporation Particules de mousse de polyuréthane thermoplastique et procédé de fabrication d'un article moulé à partir de particules de mousse de polyuréthane thermoplastique
US20190345284A1 (en) * 2016-11-14 2019-11-14 Basf Se Expanded thermoplastic polyurethane beads, production thereof and production of a molded part
EP3578068A1 (fr) * 2017-01-31 2019-12-11 ASICS Corporation Élément semelle et chaussure
CN110003635A (zh) * 2019-03-29 2019-07-12 江南大学 一种发泡热塑性聚氨酯弹性体、制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HANDBOOK OF THERMOPLASTIC ELASTOMERS, June 2014 (2014-06-01)

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