Expanded thermoplastic polyurethanes for special molding processes

Abstract

The invention relates to a molded body comprising expanded particles fused using an electromagnetic field, the expanded particles containing a composition (C1) comprising a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), the composition (C1) having a factor JDIM in the range of 0.3 to 3, the factor is defined by the melting point of the composition (C1) and the loss factor tan [delta] of the components of the composition (C1). The invention also relates to a method for producing a molded body comprising expanded particles comprising a composition (C1), comprising the steps of loading the expanded particles comprising the composition (C1) into a mold, and fusing the expanded particles comprising a thermoplastic elastomer by supplying energy at least partially via an electromagnetic field, wherein the composition (C1) has a factor JDIM in the range of 0.3 to 3. The invention also relates to the use of the molded body in soles, sole parts, midsoles, insoles, damping elements, cushioning elements, pads, grips, floors, mattresses, sporting goods, bicycle saddles, tires and in motor vehicle interior and exterior trim parts.

Description

[0001] This invention relates to a molded body comprising expanded particles fused using an electromagnetic field, the expanded particles containing a composition (C1) comprising a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein the composition (C1) has a factor JDI in the range of 0.3 to 3. M This factor is defined by the melting point of the composition (C1) and the loss factor tanδ of the components of the composition (C1). The invention also relates to a method for preparing a molded body comprising expanded particles containing the composition (C1), the method comprising the steps of: loading the expanded particles containing the composition (C1) into a mold, and fusing the expanded particles containing a thermoplastic elastomer by supplying energy at least partially via an electromagnetic field, wherein the composition (C1) has a factor JDI in the range of 0.3 to 3. M The present invention also relates to the use of the molded body in shoe soles, shoe sole parts, shoe midsoles, shoe insoles, shock-absorbing elements, cushioning elements, padding, grips, flooring, mattresses, sporting goods, bicycle saddles, tires, and in automotive interior and exterior parts.

[0002] WO2014 / 198779 A1 describes the preparation of expanded thermoplastic elastomer bead foam using extrusion technology, but does not explain the preparation of parts from expanded thermoplastic elastomer beads.

[0003] WO2015 / 052265 also describes the preparation of expanded beads from thermoplastic elastic polymers by impregnating a dense material in an autoclave. The impregnated beads can then be foamed, and in special cases, the pressure inside the autoclave can be reduced to directly mold them into parts. Alternatively, the impregnated beads can be removed and heated to the foaming temperature in a separate machine. In the case of obtaining individual foamed beads, the part preparation is not further described.

[0004] Beaded foams, such as polypropylene or polystyrene beads, are typically fused together in automated molding machines using superheated steam to form molded parts, for example, for use in the packaging industry. TPU beaded foams can be further processed not only by superheated steam fusion but also by in-situ foaming or bonding with reactive polyurethane systems. Due to the very high energy requirements of superheated steam fusion, alternatives are sought. Fusion by hot air is possible in principle, but unsatisfactory parts cannot be produced due to unsatisfactory distribution, and long cycle times are required due to the low energy content of hot air and the poor thermal conductivity of closed-cell foams.

[0005] DE102013110242 A1 describes the molding of expanded thermoplastic polyurethane bead foam. Here, different variations of the filling mold are explained, all of which are designed to have fully filled cavities. Therefore, it is mentioned that filling under pressure or sealing cracks before molding is performed. In all these variations, filling is achieved by pressing more material into the cavity, thereby increasing the overall weight and density of the part. Regarding molding, steam molding is used.

[0006] For different expanded thermoplastic beads, the use of electromagnetic radiation or electromagnetic fields to provide energy for molding is generally described in EP3698949 A1 and WO2017 / 125410A1. In particular, WO2017 / 125410A1 shows that uniformly foamed parts can be obtained by applying energy using an electromagnetic field.

[0007] A special mold design is described in EP3808522 A1, which uses electromagnetic fields to improve molding. Here, the mold is separated in the cavity to modulate the electromagnetic field and improve the uniformity of the molding.

[0008] Foam moldings containing expanded thermoplastic polyurethane are widely used in sportswear, shoes and shoe parts, as well as for cushioning elements.

[0009] The method of thermally bonding foam beads together is through high-frequency fusion, as described in particular in WO 2001 / 64414. In high-frequency fusion, the foam beads to be fused together, especially expandable polystyrene (EPS), expanded polypropylene (EPP), or expandable polyethylene terephthalate (EPET), are surrounded by a liquid medium (e.g., water) that absorbs electromagnetic radiation, and then bonded together by applying a form of electromagnetic radiation (e.g., microwaves). This method is only slightly possible for foam beads containing thermoplastic elastomers due to water absorption caused by the high polarity of thermoplastic polymers. Furthermore, temperatures of 100°C, achievable by boiling water at atmospheric pressure, are generally insufficient to fuse elastomer beads together. Water absorption allows excessive water penetration into the beads, and heating is effective not only at the contact points but also within the beads. Therefore, the beads may collapse before fusion.

[0010] DE 10 2013 012 515 A1 describes a method for thermally bonding foam beads (especially EPP or EPS) by induction heating with an improved energy balance. However, a prerequisite for producing molded parts by induction heating is that the bead parts, at least on the surfaces to be bonded, have some electrical conductivity. This can be achieved by coating with conductive fillers such as metal powders or carbon black, or nanotubes. Spraying is an example of a possible way to coat the beads.

[0011] WO 2019 / 162172 A1 discloses a method for producing beaded foam from thermoplastic elastomer-based foam beads, the method comprising wetting the foam beads with a polar liquid and bonding them together in a mold via high-frequency electromagnetic radiation. The use of additives in the molding process makes the method less efficient and increases costs.

[0012] WO 2017 / 125410 A1 relates to a method for producing granular foam parts, wherein foam particles are heated in a mold to fuse them together. The foam particles are made of polyurethane (PU), polylactic acid (PLA), polyethylene block amide (PEBA), or polyethylene terephthalate (PET). Heat is directed to the foam particles via electromagnetic RF radiation. In the case of large or thick granular foam parts, it is described that they are heated more intensely in the central region than in the edge regions. An increase in energy input via the electromagnetic field causes the foam particles in the central region of the granular foam part to completely melt.

[0013] The problem solved by the present invention is to remedy the above-mentioned disadvantages and provide a simple and cost-effective method for producing molded bodies.

[0014] According to the present invention, this problem is solved by a molded body comprising expanded particles fused using an electromagnetic field, the expanded particles containing a composition (C1) comprising a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein the composition (C1) has a content of 0.3 <JDI M Factor JDI in the range of <3 M :

[0015]

[0016] Here, 'i' is an index of the component in the composition.

[0017] Where T m The melting temperature (M) was determined by DSC based on DIN EN ISO 11357-3:2013, with a heating rate of 20 K / min and the sample dried at 100 °C under nitrogen for 10 minutes before the start of the measurement. It was determined at the maximum enthalpy point at the first peak during the first heating cycle.

[0018] tanδ is the energy dielectric loss factor of a composition measured at 80°C and 27MHz according to DIN EN IEC 62631-2-2:2022.

[0019] c is the concentration of the components in the composition, expressed as a weight percentage.

[0020] Due to the heat distribution within the mold, using an electromagnetic field to fuse the expanded particles produces a different structure within the molded body compared to molded bodies obtained by applying heat through different methods (such as, for example, steam) to fuse the expanded particles. In the latter case (steam molding), heat is primarily applied to the surface of the molded body, resulting in stronger fusion near the surface compared to the interior of the molded body.

[0021] The present invention also relates to a method for preparing a molded article comprising expanded particles containing a composition (C1), the method comprising the following steps:

[0022] (i) Loading expanded particles containing composition (C1) into a mold,

[0023] (ii) The expanded particles containing the thermoplastic elastomer are fused together by supplying energy, at least partially via an electromagnetic field.

[0024] The composition (C1) comprises a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein the composition (C1) has a content of 0.3 <JDI M Factor JDI in the range of <3 M :

[0025]

[0026] Here, 'i' is an index of the component in the composition.

[0027] Where T m The melting temperature (M) was determined by DSC based on DIN EN ISO 11357-3:2013, with a heating rate of 20 K / min and the sample dried at 100 °C under nitrogen for 10 minutes before the start of the measurement. It was determined at the maximum enthalpy point at the first peak during the first heating cycle.

[0028] tanδ is the energy dielectric loss factor of a composition measured at 80°C and 27MHz according to DIN EN IEC 62631-2-2:2022.

[0029] c is the concentration of the components in the composition, expressed as a weight percentage.

[0030] Dielectric properties define the interaction between the RF field and the material. Higher losses will lead to higher temperature rise, directly affecting molding performance. Dielectric properties are described by the real and imaginary parts of the relative permittivity ε. r =ε' r -jε“ rThe real part corresponds to the material's ability to store electric field energy, while the imaginary part corresponds to dielectric loss. The so-called loss factor tan(δ) is defined as the ratio of the imaginary to the real part of the dielectric constant (ε0). r / ε' r The practical implications become clear when comparing an ideal capacitor and a real capacitor. For an ideal capacitor, the current and voltage will have a 90° phase delay. This phase delay is less than 90° by the loss angle δ.

[0031] There are various methods for measuring the dielectric properties of materials. The choice of method depends on the desired frequency, sample geometry, and expected dielectric parameters. Measurement guidelines for solid dielectrics are described in DIN ENIEC 62631-2-2:2022. Unless otherwise specified, measurements for the values ​​described in this invention are performed using an impedance analyzer (Keysight E4991B) and a dedicated sample test fixture (16453A), which allows dielectric evaluation from 1 MHz to 1 GHz over a temperature range of -55°C to +150°C. The test fixture is placed in a laboratory oven to perform dielectric characterization within the temperature range expected during the molding process. The system is calibrated using open-circuit, short-circuit, and load (with PTFE) compensation prior to measurement.

[0032] It has been surprisingly discovered that using compositions comprising thermoplastic elastomers with a defined ratio of the melt temperature of the composition to the loss factor tanδ allows for the fusion of expanded particles and the acquisition of molded articles with improved mechanical properties. It has been found that a temperature rise caused by energizing the thermoplastic elastomer at least partially via an electromagnetic field is sufficient to induce thermomolding of the particles without melting the foam particles in the central region of the particles. Energizing the thermoplastic elastomer at least partially via an electromagnetic field enables better energy distribution during the fusion step, which in turn results in better mechanical properties of the molded article, such as better tensile strength.

[0033] According to the present invention, specific adjustments to the melt temperature and dielectric properties of the composition improve fusion during the use of an electromagnetic field and enhance the properties of the molded body obtained when stimulated by an electromagnetic field. It has been surprisingly found that the melt temperature of the composition strongly depends on the melt temperature of the thermoplastic elastomer used as component (M), and the dielectric loss factor depends on the dielectric properties of components (M) and (B1) present in the composition. Therefore, according to the present invention, the properties of the composition can be adjusted using different combinations of components and based on formulation adjustments as defined above.

[0034] According to the present invention, the composition (C1) comprises at least one thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1). The composition may contain additional components or additives. Typically, the composition (C1) comprises 50% to 100% by weight of the thermoplastic elastomer (TPE1) based on the weight of the composition (C1), preferably 60% to 99% by weight, more preferably 70% to 98% by weight, particularly in the range of 85% to 97% by weight, and more preferably in the range of 90% to 95% by weight.

[0035] Useful thermoplastic elastomers include, for example, thermoplastic polyurethane (TPU), thermoplastic polyester elastomers (e.g., polyether esters and polyester esters), thermoplastic copolyamides (e.g., polyether copolyamides), or thermoplastic styrene-butadiene block copolymers. Foam beads based on thermoplastic polyurethane (TPU) are particularly preferred.

[0036] According to the present invention, composition (C1) has a content of 0.3 <JDI M Factor JDI in the range <3 M :

[0037]

[0038] Here, 'i' is an index of the component in the composition.

[0039] Where T m The melting temperature (M) was determined by DSC based on DIN EN ISO 11357-3:2013, with a heating rate of 20 K / min and the sample dried at 100 °C under nitrogen for 10 minutes before the start of the measurement. It was determined at the maximum enthalpy point at the first peak during the first heating cycle.

[0040] tanδ is the energy dielectric loss factor of a composition measured at 80°C and 27MHz according to DIN EN IEC 62631-2-2:2022.

[0041] c is the concentration of the components in the composition, expressed as a weight percentage.

[0042] Typically, the melting temperature of the composition (C1) is in the range of 90°C to 170°C, more preferably in the range of 100°C to 160°C, and especially in the range of 110°C to 140°C.

[0043] The thermoplastic elastomer used for producing foam beads preferably has a Shore hardness in the range of 70A to 92A, more preferably in the range of 75A to 90A, and even more preferably in the range of 80A to 90A, measured by DIN ISO 48-4:2021-02 (average value; indentation 3s) using samples that have been tempered at 100°C for 20 hours after preparation.

[0044] The bulk density of the foam beads used is preferably 30 kg / m³. 3 Up to 250kg / cm 3 Within the range.

[0045] The expanded thermoplastic polyurethane beads according to the present invention belong to the granular foam group, also known as expanded granules (or beaded foam, granular foam, expanded thermoplastic elastomer granules, or expanded thermoplastic polyurethane beads). Granular foams based on thermoplastic polyurethane or other thermoplastic elastomers and molded articles (also known as molded articles) made from them are known (e.g., WO 94 / 20568A1, WO 2007 / 082838 A1, WO2017 / 030835 A1, WO 2013 / 153190A1, WO2010 / 010010A1) and can be used in many ways.

[0046] In the context of this invention, foamed beads or granular foam or beaded foam refers to foam in granular form, with the average length of the particles preferably in the range of 1 mm to 15 mm, as determined according to DS / ISO 13322-2:2021. In the case of non-spherical particles, such as elliptical particles, the average length refers to the longest dimension. (Determined by 3D evaluation of fine particles, for example, by dynamic image analysis using an optical measurement device called "PartAn 3D" by Microtrac).

[0047] The single-foam particles according to the invention preferably have an average mass in the range of 0.1 mg to 50 mg, more preferably in the range of 0.5 mg to 45 mg. In this context, average mass means the arithmetic mean based on a sample size of 10 different particles, wherein each particle is weighed three times.

[0048] The foamed granules according to the invention typically have a bulk density of 30 g / l to 250 g / l, preferably 50 g / l to 200 g / l, and more preferably 70 g / l to 180 g / l. Bulk density is measured similarly to DIN ISO 60:1999, except that the above values ​​are determined using a 101-volume container instead of a 0.11-volume container, because a measurement of only 0.11 volumes is too inaccurate, especially for low-density and low-mass foamed granules.

[0049] The particulate foam according to the invention can optionally be optimized by additives such as dyes, processing aids, nucleating agents, or stabilizers. The additives can be added during the formation of the particulate foam precursor or during the foaming step. The precursor is a polymer composition used as an input material for foaming.

[0050] Suitable additives may be present in the composition in amounts from 0.01% to 15% by weight, preferably from 0.1% to 10% by weight, and especially from 0.5% to 5% by weight, in each case based on the weight of the composition (C1).

[0051] In another embodiment of the invention, particulate foam can be coated.

[0052] In a preferred embodiment of the granular foam molded article according to the invention, expanded thermoplastic polyurethane beads with the same composition and the same average mass are used.

[0053] In a preferred embodiment, the granular foam molded article consists of expanded thermoplastic polyurethane beads.

[0054] According to another aspect, the present invention also relates to the methods disclosed above, wherein the thermoplastic elastomer is thermoplastic polyurethane.

[0055] In a preferred embodiment, the thermoplastic polymer, particularly a thermoplastic polyurethane present as component (M) in the composition, has a dielectric loss factor in the range of 0.04 to 0.2 at 27 MHz and 80 °C. The dielectric loss factor of the thermoplastic polymer (TP1) or other additives can vary over a wide range. For example, thermoplastic polymers such as polystyrene or polyolefins have a dielectric loss factor of about 0.

[0056] In the context of this invention, unless otherwise stated, the dielectric loss factor is determined using either the dense material (i.e., the material prior to the foaming step) or the separate material of the foam beads after they have been melted and annealed to obtain the dense material. The dielectric loss factor can be measured using a dielectric material testing fixture called Keysight, as described above. For this purpose, small, compact sheets must be produced by injection molding and then cut into pieces that can be placed in the dielectric testing fixture.

[0057] According to the present invention, the expanded particles are fused together by supplying energy, at least partially, via an electromagnetic field. The heat generated by stimulating the thermoplastic elastomer is sufficient to cause thermal bonding of the foam beads.

[0058] Typically, the thermal bonding of foam beads in a mold is achieved via high-frequency electromagnetic radiation, particularly via microwaves. High frequency should be understood as electromagnetic radiation with a frequency of not less than 100 MHz. The electromagnetic radiation used is generally in the frequency range between 100 MHz and 300 GHz. Microwaves with a frequency range between 0.5 GHz and 100 GHz are preferred, more preferably 0.8 GHz to 10 GHz, and an irradiation time between 0.1 minutes and 15 minutes are used. The frequency range of the microwaves is preferably consistent with the absorption behavior of the thermoplastic elastomer, or conversely, the thermoplastic elastomer is selected based on the intensity of its absorption behavior relative to the frequency range of the microwave equipment used.

[0059] The method of the present invention enables foam beads to be fused together over a very wide frequency range.

[0060] Energy can be provided via electromagnetic induction. For this purpose, a dielectric molding tool is placed between at least two capacitor plates that generate at least one dielectric field. Expanded foam beads are loaded into the cavity of the molding tool and heated by applying the dielectric field. Consequently, the surface of the foam beads partially melts, causing the beads to fuse and form a molded part. To maintain the foam shape and melt only the bead surface, the method is adjusted according to the material used and the design of the molded part. Typically, the temperature within the mold is in the range of 40°C below the melt temperature of the composition (C1) to 20°C above the first melt temperature of the composition (C1), preferably in the range of 20°C below the melt temperature of the composition (C1) to 10°C above the first melt temperature of the composition (C1), and particularly in the range of 10°C below the melt temperature of the composition (C1) to 5°C above the first melt temperature of the composition (C1). The temperature within the mold can be measured, for example, using an optical sensor.

[0061] Typically, the energy input is controlled and adjusted by the applied voltage, irradiation time, and material quantity. The molded part must be stabilized and cooled before it can be removed from the molding tool. Stabilization can be achieved by stopping active heating or by an active cooling process, as described, for example, in EP3405322.

[0062] Fusion via energy radiation typically occurs in the microwave frequency range of 300 MHz to 300 GHz or in the radio frequency range of 30 kHz to 300 MHz. Microwaves are preferably applied in the frequency range between 0.5 GHz and 100 GHz, particularly preferably between 0.8 GHz and 10 GHz, and the irradiation time is between 1 second and 15 minutes. Radio waves are preferably applied in the frequency range between 500 kHz and 100 MHz, particularly preferably between 1 MHz and 100 MHz, and the irradiation time is between 1 second and 30 minutes.

[0063] According to another aspect, the invention also relates to the method disclosed above, wherein in step (ii), the frequency of the electromagnetic field is in the range of 1 MHz to 100 MHz, particularly in the range of 25 MHz to 30 MHz. Typically, the irradiation time in step (ii) is in the range of 1 second to 300 seconds.

[0064] According to the invention, the molded body typically has an average thickness in the range of 0.01 cm to 30 cm, preferably in the range of 0.1 cm to 15 cm, more preferably in the range of 0.5 cm to 10 cm, and especially in the range of 1 cm to 5 cm.

[0065] Typically, the conditions in step (ii), such as the material of the mold, the distance between the plates, and the frequency range used, are adapted to generate an electric field of about 0.2 kV / cm to 3 kV / cm.

[0066] The properties of the composition (C1) and the thermoplastic elastomers and thermoplastic polymers used can be varied over a wide range, as long as JDI M Within the range defined above, suitable thermoplastic elastomers may be used, for example, having a molecular weight Mw in the range of 50 kg / mol to 250 kg / mol. Preferably, the molecular weight Mw is in the range of 60 kg / mol to 200 kg / mol, and particularly in the range of 100 kg / mol to 180 kg / mol.

[0067] Unless otherwise stated, the molecular weight (Mw) of the thermoplastic elastomer is determined using GPC in the context of this invention. Unless otherwise stated in the context of this invention, the weight-average molecular weight (Mw) of the thermoplastic elastomer dissolved in HFIP (hexafluoroisopropanol) is determined by GPC using the thermoplastic elastomer dissolved in HFIP (hexafluoroisopropanol). The molecular weight determination is performed using two GPC columns arranged in series (PSS-gel; 100A; 5μm; 300*8mm, Jordi-Gel DVB; MixedBed; 5μm; 250*10mm; column temperature 60°C; flow rate 1mL / min; RI detector). Calibration is performed using polymethyl methacrylate (EasyCal; from PSS, Mainz), and HFIP is used as the eluent.

[0068] Expanded particles containing thermoplastic elastomers and methods for their preparation are known in principle in the prior art. Specifically, expanded particles containing thermoplastic polyurethane are known in the prior art.

[0069] Typically, molecular weight can be adjusted by methods known to those skilled in the art, such as by adjusting process parameters during preparation, the ratio of raw materials used, or the reactivity of the raw materials used.

[0070] Thermoplastic polyurethanes are typically prepared using at least one polyisocyanate, at least one polyol, and usually at least one chain extender. The components suitable for preparing thermoplastic polyurethanes are, in principle, known to those skilled in the art.

[0071] In the context of this invention, suitable isocyanates, particularly diisocyanates, especially aliphatic or aromatic diisocyanates, more preferably aliphatic diisocyanates.

[0072] Furthermore, in the context of this invention, the pre-reaction product can be used as the isocyanate component, wherein some of the OH components have already reacted with the isocyanate in the aforementioned reaction steps. The resulting product reacts with the remaining OH components in subsequent steps, i.e., the actual polymer reaction, to form a thermoplastic polyurethane.

[0073] The aliphatic diisocyanates commonly used are conventional aliphatic and / or cyclic aliphatic diisocyanates. Suitable aromatic diisocyanates are also known to those skilled in the art.

[0074] In principle, mixtures can also be used. An example of a mixture is one containing at least one additional methylene diphenyl diisocyanate besides methylene diphenyl 4,4′-diisocyanate. The term "methylene diphenyl diisocyanate" here refers to diphenylmethane 2,2′-diisocyanate, diphenylmethane 2,4′-diisocyanate, and / or diphenylmethane 4,4′-diisocyanate, or a mixture of two or three isomers. Therefore, for example, diphenylmethane 2,2′-diisocyanate or diphenylmethane 2,4′-diisocyanate, or a mixture of two or three isomers, can be used as an additional isocyanate. In this embodiment, the polyisocyanate composition may also contain other polyisocyanates described above.

[0075] If other isocyanates are used, these isocyanates are present in the isocyanate composition (IC) in amounts preferably from 0.1% to 20% by weight, more preferably from 0.1% to 10% by weight, and particularly preferably from 0.5% to 5% by weight.

[0076] Preferred examples of higher-functionality isocyanates are triisocyanates, such as triphenylmethane 4,4′,4″-triisocyanate, and cyanurate esters of the above diisocyanates, as well as oligomers that can be obtained by partial reaction of diisocyanates with water, such as biuret of the above diisocyanates, and oligomers that can be obtained by controlled reaction of semi-terminated diisocyanates with polyols having an average of more than two, and preferably three or more, hydroxyl groups.

[0077] The organic isocyanates that can be used are aliphatic, cycloaliphatic, aryliphatic, and / or aromatic isocyanates.

[0078] Alternatively, crosslinking agents can be used, such as the aforementioned higher-functionality polyisocyanates or polyols, or other higher-functionality molecules having multiple isocyanate reactive functional groups. Within the context of this invention, crosslinking of the product can also be achieved by using an excess of isocyanate groups in proportion to the hydroxyl groups. Examples of higher-functionality isocyanates are triisocyanates, such as triphenylmethane 4,4′,4″-triisocyanate and isocyanurate, as well as cyanurate esters of the aforementioned diisocyanates, and oligomers obtainable through partial reaction of diisocyanates with water, such as biuret of the aforementioned diisocyanates, and oligomers obtainable through controlled reaction of semi-terminated diisocyanates with polyols having an average of more than two, and preferably three or more, hydroxyl groups.

[0079] Here, in the context of the present invention, based on the total mixture of components, the amount of crosslinking agent, i.e., the amount of higher-functionality isocyanate and higher-functionality polyol or higher-functionality chain extender, is no more than 3% by weight, preferably less than 1% by weight, and more preferably less than 0.5% by weight.

[0080] The polyisocyanate composition may also contain one or more solvents. Suitable solvents are known to those skilled in the art. Suitable examples are non-reactive solvents such as ethyl acetate, methyl ethyl ketone, and hydrocarbons.

[0081] According to the invention, a polyol composition (PC) can be used. According to the invention, the polyol composition (PC) may contain at least one polyol. Suitable polyols are known in principle to those skilled in the art and are described, for example, in "Kunststoffhandbuch [Plastics Handbook], Volume 7, Polyurethane [Polyurethanes]", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. Polyester alcohols or polyether alcohols are particularly preferred as polyols. Polycarbonates can also be used. Copolymers can also be used in the context of the invention. Polyether polyols are particularly preferred. The number average molecular weight of the polyol used according to the invention is preferably in the range of 500 g / mol to 5000 g / mol, for example in the range of 550 g / mol to 2000 g / mol, preferably in the range of 600 g / mol to 1500 g / mol, particularly between 650 g / mol and 1000 g / mol. According to the invention, the polyol used may be a fossil-based polyol or a non-fossil polyol.

[0082] According to the present invention, polyether alcohols, as well as polyester alcohols, block copolymers, and hybrid polyols such as, for example, poly(ester / amide) are suitable. According to the present invention, preferred polyether alcohols are polyethylene glycol and polypropylene glycol. Suitable polyols may also be selected from polyadipate, polycarbonate, polycarbonate diol, and polycaprolactone.

[0083] In another embodiment, the invention therefore relates to foamed granules as previously described, wherein the polyol composition comprises a polyol selected from the group consisting of polyether alcohols, polyester alcohols such as polycaprolactone polyols and polycarbonate polyols.

[0084] Suitable polyols are, for example, those having ether and ester blocks, such as polycaprolactone having polyethylene oxide or polypropylene oxide terminal blocks, or polyether having polycaprolactone terminal blocks. According to the invention, preferred polyether alcohols are polyethylene glycol and polypropylene glycol. Suitable polyols are, for example, polytetramethylene glycol or polytrimethylene glycol. Polycaprolactone is also preferred. According to the invention, polyester alcohols, particularly non-fossilized polyester alcohols, can also be used. Suitable polyester alcohols are, for example, based on succinic acid. Castor oil-based polyols or lignin-based polyols can also be used.

[0085] According to the invention, mixtures of different polyols can also be used. Preferably, the average functionality of the polyol / polyol composition used is between 1.8 and 2.3, more preferably between 1.9 and 2.2, and particularly 2. Preferably, the polyol used according to the invention has only primary hydroxyl groups.

[0086] In one embodiment of the invention, a polyol composition (PC) comprising at least polytetrahydrofuran is used. According to the invention, in addition to polytetrahydrofuran, the polyol composition may also comprise other polyols.

[0087] According to the invention, suitable other polyols include, for example, polyethers, polyesters, block copolymers, and hybrid polyols such as, for example, poly(ester / amide). Suitable block copolymers are, for example, those having ether and ester blocks, such as polycaprolactone having polyethylene oxide or polypropylene oxide terminal blocks, or polyether having polycaprolactone terminal blocks. According to the invention, preferred polyether alcohols are polyethylene glycol and polypropylene glycol. Polycaprolactone is also preferred as another polyol.

[0088] According to the present invention, non-fossil-based polytetramethylene glycol or polytrimethylene glycol, or a mixture of fossil and non-fossil-based polyols, may also be used.

[0089] In a particularly preferred embodiment, the polytetrahydrofuran has a number-average molecular weight Mn in the following range: from 500 g / mol to 5000 g / mol, preferably from 500 g / mol to 2000 g / mol, more preferably from 550 g / mol to 2000 g / mol, and particularly preferably from 650 g / mol to 1400 g / mol.

[0090] Within the context of this invention, the composition of the polyol composition (PC) can vary over a wide range. The polyol composition may also comprise a mixture of various polyols.

[0091] According to the present invention, the polyol composition may further contain a solvent. Suitable solvents are known to those skilled in the art.

[0092] When polytetrahydrofuran is used, the number-average molecular weight Mn of the polytetrahydrofuran is preferably in the range of 500 g / mol to 2000 g / mol. More preferably, the number-average molecular weight Mn of the polytetrahydrofuran is in the range of 650 g / mol to 1400 g / mol.

[0093] In another embodiment, the invention also relates to foamed granules as previously described, wherein the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofuran having a number-average molecular weight Mn in the range of 500 g / mol to 5000 g / mol.

[0094] In another embodiment, the invention therefore relates to foamed granules as previously described, wherein the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofuran having a number-average molecular weight Mn in the range of 500 g / mol to 2000 g / mol.

[0095] According to the present invention, mixtures of various polytetrahydrofurans, i.e. mixtures of polytetrahydrofurans with different molecular weights, can also be used.

[0096] Preferred polyether alcohols of the present invention are polyethylene glycol, polypropylene glycol, and polytetrahydrofuran, as well as mixtures thereof. According to the present invention, mixtures of various polytetrahydrofurans with different molecular weights may also be used, for example.

[0097] According to the present invention, at least one chain extender (CE1) may be used. Suitable chain extenders are known to those skilled in the art. For example, chain extenders are compounds having two groups reactive to isocyanate groups, particularly those with a molecular weight of less than 500 g / mol. Suitable chain extenders are, for example, diamines or diols. According to the present invention, diols are more preferred. Within the scope of the present invention, mixtures of two or more chain extenders may also be used.

[0098] Suitable diols are known in principle to those skilled in the art. According to the invention, the diol preferably has a molecular weight of <500 g / mol. According to the invention, aliphatic, aryliphatic, aromatic, and / or cycloaliphatic diols with molecular weights from 50 g / mol to 220 g / mol can be used here as chain extenders. Alkyl diols having 2 to 10 carbon atoms in the alkylene group are preferred, particularly dialkylene diols, trialkylene diols, tetraalkylene diols, pentaalkylene diols, hexaalkylene diols, heptaalkylene diols, octaalkylene diols, nonaalkylene diols, and / or decaalkylene diols. For the present invention, 1,2-ethylene glycol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, and hexane-1,6-diol are particularly preferred.

[0099] In the context of this invention, suitable chain extenders (CE1) are also branched compounds, such as 1,4-cyclohexanediol, 2-butyl-2-ethylpropanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol, pinacol, 2-ethylhexane-1,3-diol, or cyclohexane-1,4-diol.

[0100] In another embodiment, the invention therefore relates to foamed granules as previously described, wherein the chain extender (CE1) is selected from the group consisting of: propane-1,3-diol, ethane-1,2-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, and HQEE.

[0101] According to another aspect, the present invention also relates to the method disclosed above, wherein the thermoplastic polyurethane is obtained or can be obtained by reacting at least components (a) to (c):

[0102] (a) A polyisocyanate composition (IC) comprising an isocyanate selected from methylene diphenyl diisocyanate, hexamethylene diisocyanate and pentamethylene diisocyanate;

[0103] (b) at least one chain extender (CE1),

[0104] (c) Polyol composition (PC).

[0105] The properties of the obtained thermoplastic polyurethane, especially its molecular weight, can be adjusted, for example, by regulating the temperature applied during the preparation process. Generally, lower temperatures result in lower molecular weights. Furthermore, the use of a suitable catalyst and the amount of catalyst used can affect the molecular weight of the resulting thermoplastic polyurethane. The molecular weight of the obtained thermoplastic polyurethane can also be adjusted by the ratio of the components used, particularly the ratio of NCO groups to groups reactive with isocyanate groups.

[0106] Preferably, the quantitative ratio of the components used is selected such that a hard segment content is obtained in the range of 5% to 80%, preferably in the range of 10% to 55%, particularly in the range of 13% to 45%, and more preferably in the range of 15% to 35%. Unless otherwise stated, this hard segment content is calculated according to formula (I):

[0107]

[0108] Thermoplastic polyurethanes with a molecular weight (Mw) in the range of 50 kg / mol to 250 kg / mol and a hard segment content in the range of 15% to 50% have been found to be particularly suitable for preparing molded parts.

[0109] According to another aspect, the present invention also relates to the method disclosed above, wherein the hard segment content of the thermoplastic polyurethane is in the range of 15% to 50%, the hard segment content being calculated according to formula (I):

[0110]

[0111] Furthermore, it has been found that the crystallinity of thermoplastic elastomers can affect the properties of the resulting molds. Thermoplastic elastomers, particularly thermoplastic polyurethanes with low crystallinity, have been found to be particularly suitable for preparing molded bodies. Crystallinity can be determined by DSC measurement according to DIN EN ISO 11357-3:2018, comprising a drying step of 100°C for 10 minutes within the measuring system from below 0°C to 250°C before the start of measurement, wherein the cooling rate to reach the initial temperature of measurement is 20 K / min, and the heating rate from the initial temperature to 250°C is 10 K / min.

[0112] According to the invention, composition (C1) further comprises at least one thermoplastic polymer (TP1) as component (B1). Composition (C1) may also comprise additional components, such as another thermoplastic polymer (TP2) or (TP3) as components (B2) and (B3). Suitable thermoplastic polymers are known in principle to those skilled in the art. Suitable ones are, for example, thermoplastic polymers such as polyamides, styrene polymers, or polyolefins such as polyethylene or polypropylene.

[0113] According to another embodiment, the present invention also relates to the method disclosed above, wherein the thermoplastic polymer (TP1) is selected from the group consisting of polyolefins, polyamides and polystyrene.

[0114] Suitable polyamides are commercially available polyamides and are known in principle to those skilled in the art.

[0115] Suitable styrene polymers may be standard polystyrene. The term "standard polystyrene" preferably encompasses atactic polystyrene, syndiotactic polystyrene, or isotactic polystyrene, more preferably atactic polystyrene. The atactic polystyrene of the present invention is amorphous and has a glass transition temperature in the range of 100°C ± 20°C (determined by the inflection point method according to DIN EN ISO 11357-1, February 2017 / DIN EN ISO 11357-2, July 2014). The syndiotactic and isotactic polystyrene of the present invention are each semi-crystalline and have melting points in the ranges of 270°C and 240°C, respectively (DIN EN ISO 11357-1, February 2017 / DIN EN ISO 11357-3, April 2013, peak melting temperatures). The polystyrene used typically has a tensile modulus of elasticity exceeding 2500 (DIN EN ISO527-1 / 2, June 2012).

[0116] The production and processing of polystyrene according to the present invention are extensively described in the literature, for example Becker / Braun (1996) Kunststoff-Handbuch Band 4, “Polystyrol” [Plastics handbook, Vol. 4, “Polystyrene”].

[0117] Suitable alternatives include styrene polymers with an elastic modulus below 2700 MPa (DIN EN ISO 527-1 / 2, June 2012), preferably styrene block copolymers based on styrene monomers. Suitable alternatives include, for example, styrene-based thermoplastic elastomers and high-impact polystyrene (HIPS), which includes, by way of example, SEBS, SBS, SEPS, SEPS-V and acrylonitrile-butadiene-styrene copolymer (ABS), with high-impact polystyrene (HIPS) being particularly preferred.

[0118] The production and processing of styrene polymers are extensively described in the literature, for example, Becker / Braun (1996) Kunststoff-Handbuch Band 4, “Polystyrol” [Plastics handbook, Vol. 4, “Polystyrene”].

[0119] Suitable polyolefins include, for example, homopolymer polypropylene, polyethylene, or a mixture of homopolymer polypropylene and polyethylene.

[0120] Polyolefins prepared using both Ziegler catalysts and metallocene catalysts are suitable.

[0121] The microcrystalline melting point (DIN EN ISO 11357-1 / 3, February 2017 / April 2013, W peak melting temperature) of polyolefins that can be used according to the present invention is typically 90°C to 170°C.

[0122] Suitable polyethylene can be polyethylene polymers commonly used by those skilled in the art, such as LD (low density), LLD (linear low density), MD (medium density), or HD (high density), HMW (high molecular weight), or UHMW (ultra-high molecular weight) polyethylene.

[0123] The thermoplastic polymer (TP1) may be present in the composition in an amount of 0.01% to 20% by weight, preferably in an amount of 0.1% to 15% by weight, and especially in an amount of 1% to 10% by weight, in each case based on the weight of the composition (C1).

[0124] In the context of this invention, two or more thermoplastic polymers may also be used. Preferably, the total amount of thermoplastic polymer in the composition (C1) is from 0.01% to 20% by weight, more preferably from 0.1% to 15% by weight, and especially from 1% to 10% by weight, in each case based on the weight of the composition (C1).

[0125] According to the present invention, the amount of thermoplastic polymer can be adapted to adjust the composition factor JDIM. The thermoplastic polymer and the amount used can be selected according to the dielectric loss factor of the thermoplastic elastomer (TPE1) and the dielectric loss factor of the thermoplastic polymer (TP1).

[0126] The composition (C1) contains a thermoplastic elastomer and a thermoplastic polymer, but may also contain suitable amounts of other additives, such as at least one additive selected from the group consisting of dipropylene glycol and water.

[0127] Suitable additives may also be selected from the group consisting of esters of carboxylic acids and diols or triols, such as ethylene glycol esters of acetic acid or citric acid, glycerides of acetic acid or citric acid or diols and liquid polydiols, such as triethylene glycol or tripropylene glycol, for example 1,2,3-propanetriol triacetate (triacetin, glyceryl triacetate), triethylene glycol or tripropylene glycol.

[0128] These additives may be present in the composition in amounts from 0.01% to 10% by weight, preferably from 0.01% to 5% by weight, and especially from 0.01% to 25% by weight, in each case based on the weight of the composition (C1).

[0129] In the context of this invention, metal fibers or carbon fibers may also be used as additives.

[0130] In one embodiment of the invention, the particulate foam contains polar additives that enhance the dielectric heating effect by absorbing electromagnetic radiation. The polar additives are preferably selected from the group consisting of: inorganic salts, esters of carboxylic acids and diols or triols or glycols, amines, urea compounds, polyols, and glycerols.

[0131] Polymer foam beads can be coated with water or other polar liquids or additives containing functional groups and hydrocarbons (such as urea or carboxylic acids and esters of glycols or triols or glycols and liquid polyethylene glycol). Preferably, the coating is applied at a ratio of 0.1% to 10% by weight, more preferably at a ratio of 1% to 6% by weight, depending on the particulate foam used. In another embodiment of the invention, the polymer foam beads are coated with an inorganic salt solution, such as, for example, a sodium chloride solution, prior to fusion by electromagnetic radiation. Preferably, the concentration of the applied salt solution is in the range of 0.1% to 5% by weight, more preferably between 0.1% and 0.8% by weight. The above-described functionalization to increase the dielectric heating strength of non-polar polymer foam beads can be carried out in a manner similar to that described in EP3053732 or WO16146537. Typically, polar additives are applied to polymer foam beads that cannot be excited by electromagnetic radiation or cannot be sufficiently excited by electromagnetic radiation, and therefore cannot be heated without suitable additives. Therefore, the frequency range of the applied electromagnetic radiation is adjusted according to the absorption behavior of the polar coating or additive, or vice versa, the polar liquid or additive is selected based on the absorption behavior according to the available frequency range of the device used. The range of fusion polymers of the device used. The fusion of polymeric foam beads based on thermoplastic polyurethane (TPU) or thermoplastic polyamide (TPA) via electromagnetic radiation is preferably achievable in the context of this invention without the use of polar additives.

[0132] Molded parts can be prepared using a molding machine. This is done either manually by feeding the foamed granules into the molding tool or automatically using pressurized air. The molding tool (also known as a mold or molding die) consists of two main components: an injection mold with a filling nozzle and a mating plate. To create the molded part, the two molds are pressed together, forming a cavity that shapes the part. The cavity can be filled using either a crevice filling method or a pressure filling method.

[0133] The crack filling method includes the following steps:

[0134] (i') Inject expanded foam particles into the mold cavity without back pressure on the mating plate.

[0135] (ii') Weld the particles together while mechanically closing the mold plate.

[0136] (iii') Cooling the molded parts, and

[0137] (iv') Demold the produced parts.

[0138] In step (i'), the gap between the injection mold plate and the mating plate is adjusted; this gap is also referred to as the crack height. In step (i'), the mold cavity is filled with a predetermined amount of expanding beads. In step (ii'), compared to step (i'), the volume of the mold cavity is reduced because the two parts of the molding tool are tightly closed, thus eliminating the intermediate gap. This results in an increase in pressure within the mold cavity. The expanding beads thus press against each other and can therefore fuse together to obtain the molded part.

[0139] The degree of compression is an important parameter for controlling the fusion quality of molded parts. The degree of compression is calculated by dividing the volume of the dose per cycle by the volume of the mold cavity adjusted in step (ii′), where the volume of the dose per cycle is given by dividing the weight of the dose per cycle by the bulk density of the foamed beads.

[0140] In one embodiment of the invention, the degree of compression is in the range of 1.7 to 2.3. Preferably, the degree of compression in the crack filling method is less than 2.

[0141] The pressure filling method includes the following steps:

[0142] (i') Expanded foam particles are injected into the mold cavity using pneumatic pressure, while simultaneously pressing the two plates of the mold tightly together.

[0143] (ii') Fusion particles

[0144] (iii') Cooling the molded parts,

[0145] (iv') Demold the produced parts.

[0146] Since the injection pressure applied in step (i') stops in step (ii'), the inserted foam beads can expand further, thus pressing against each other and thus becoming fused together to form a molded part.

[0147] The fusion in step (ii') can be induced by at least one electromagnetic field, regardless of the chosen loading method.

[0148] According to another embodiment, the present invention also relates to the method disclosed above, wherein a crack filling method is used in step (i).

[0149] As described above, energy is provided via electromagnetic induction. For this purpose, a dielectric molding tool is placed between at least two capacitor plates that generate at least one dielectric field. Expanded foam beads are loaded into the cavity of the molding tool and heated by applying the dielectric field. Consequently, the surfaces of the foam beads partially melt, and the beads become fused to form a molded part. To maintain the foam morphology and melt only the bead surfaces, the method is tailored according to the material used and the design of the molded part. Typically, the energy input is controlled and adjusted by the applied voltage, irradiation time, and material quantity. The molded part must be stabilized and cooled before it can be removed from the molding tool. Stabilization can be achieved by stopping active heating or by an active cooling process, such as described, for example, in EP3405322.

[0150] Fusion via energy radiation typically occurs in the microwave frequency range of 300 MHz to 300 GHz or in the radio frequency range of 30 kHz to 300 MHz. Microwaves are preferably applied in the frequency range between 0.5 GHz and 100 GHz, particularly preferably between 0.8 GHz and 10 GHz, and the irradiation time is between 1 second and 15 minutes. Radio waves are preferably applied in the frequency range between 500 kHz and 100 MHz, particularly preferably between 1 MHz and 80 MHz, and the irradiation time is between 1 second and 30 minutes.

[0151] Expanded particles containing thermoplastic elastomers can be molded without the use of additional additives that can be stimulated by electromagnetic fields (especially additives that can be stimulated by electromagnetic fields to increase the temperature inside the mold). Preferably, additives that can be stimulated by electromagnetic fields in a manner that causes an increase in temperature inside the mold are not used in the method according to the invention.

[0152] According to another aspect, the present invention also relates to the method disclosed above, wherein in step (i) or (ii) no additives that can be stimulated by an electromagnetic field and cause the temperature in the mold to rise are added.

[0153] According to another aspect, the present invention also relates to the use of expanded particles containing a composition (C1), the composition comprising a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein the composition (C1) has a content of 0.3 <JDI M Factor JDI in the range of <3 M :

[0154]

[0155] Here, 'i' is an index of the component in the composition.

[0156] Where T mThe melting temperature (M) was determined by DSC based on DIN EN ISO 11357-3:2013, with a heating rate of 20 K / min and the sample dried at 100 °C under nitrogen for 10 minutes before the start of the measurement. It was determined at the maximum enthalpy point at the first peak during the first heating cycle.

[0157] tanδ is the energy dielectric loss factor of a composition measured at 80°C and 27MHz according to DIN EN IEC 62631-2-2:2022.

[0158] c is the concentration of the components in the composition, expressed as a weight percentage.

[0159] According to another aspect, the present invention also relates to molded articles that can be obtained or acquired by the methods disclosed above.

[0160] Due to their elastomeric properties, the beaded foams of the present invention can be used in applications in the fields of sports, footwear and packaging, for example, as safety footwear or as packaging for electronic components or instruments.

[0161] This invention further provides the use of the foamed granules of this invention in the production of molded bodies for use in shoe midsoles, shoe insoles, shoe assembly soles, bicycle saddles, bicycle tires, shock-absorbing elements, cushioning components, mattresses, padding, grips, protective films, in components of automotive interior and exterior parts, in balls and sports equipment, or as floor coverings, particularly for sports field surfaces, athletic field surfaces, sports stadiums, children's playgrounds, and roads. This invention also provides the use of the foamed granules of this invention in the production of parts or packaging for consumer or industrial products and in the automotive sector.

[0162] The foamed granules of the present invention are preferably used to produce molded bodies for use in shoe midsoles, shoe insoles, shoe composite soles, or cushioning elements for shoes.

[0163] Here, the shoes are preferably outdoor shoes, sports shoes, sandals, boots or safety shoes, with sports shoes being particularly preferred.

[0164] According to another aspect, the present invention also relates to the use of molded bodies obtained according to or capable of being obtained according to the methods disclosed above in shoe soles, shoe sole parts, shoe midsoles, shoe insoles, shock-absorbing elements, cushioning elements, padding, grips, flooring, mattresses, sporting goods, bicycle saddles, tires, and in automotive interior and exterior parts. According to another aspect, the present invention also relates to the use of the molded bodies disclosed above in shoe soles, shoe sole parts, shoe midsoles, shoe insoles, shock-absorbing elements, cushioning elements, padding, grips, flooring, mattresses, sporting goods, bicycle saddles, tires, and in automotive interior and exterior parts.

[0165] Further embodiments of the invention can be found in the claims and examples. It should be understood that the features described above and set forth below according to the subject matter / method / use of the invention are applicable not only to the combinations specified in each case, but also to other combinations without departing from the scope of the invention. For example, combinations of preferred features with particularly preferred features, or combinations of features not further characterized with particularly preferred features, are therefore implicitly covered, even if such combinations are not explicitly mentioned.

[0166] The following sets forth exemplary embodiments of the invention, but these are not intended to limit the invention. In particular, the invention also covers those embodiments derived from dependent references and therefore specified herein.

[0167] 1. A molded body comprising expanded particles fused using an electromagnetic field, said expanded particles containing a composition (C1) comprising a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein said composition (C1) has a content of 0.3 <JDI M Factor JDI in the range <3 M :

[0168]

[0169] Here, 'i' is an index of the component in the composition.

[0170] Where T m The melting temperature (M) was determined by DSC based on DIN EN ISO 11357-3:2013, with a heating rate of 20 K / min and the sample dried at 100 °C under nitrogen for 10 minutes before the start of the measurement. It was determined at the maximum enthalpy point at the first peak during the first heating cycle.

[0171] tanδ is the energy dielectric loss factor of the components of the composition, measured at 80°C and 27MHz according to DIN EN IEC 62631-2-2:2022.

[0172] c is the concentration of the component in the composition, expressed as a weight percentage.

[0173] 2. The molded body according to embodiment 1, wherein the thermoplastic elastomer (TPE1) is thermoplastic polyurethane.

[0174] 3. The molded body according to any one of embodiments 1 or 2, wherein the thermoplastic polymer (TP1) is selected from the group consisting of polyolefins, polyamides and polystyrene, and particularly from the group consisting of polyethylene and polystyrene.

[0175] 4. The molded body according to any one of embodiments 1 to 3, wherein the molded body has an average thickness in the range of 0.1 cm to 30 cm.

[0176] 5. The molded body according to any one of embodiments 1 to 4, wherein the molded body has a tensile strength greater than 0.6 MPa, preferably greater than 0.7 MPa, more preferably greater than 0.8 MPa, more preferably greater than 0.85 MPa, more preferably greater than 0.9 MPa, and especially greater than 1.0 MPa, as determined according to ASTM D 5035:2015.

[0177] 6. The molded body according to any one of embodiments 1 to 5, wherein the thermoplastic elastomer is a thermoplastic polyurethane with a Shore hardness in the range of 70A to 92A.

[0178] 7. A method for preparing a molded article comprising expanded particles containing a composition (C1), the method comprising the following steps:

[0179] (i) Loading the expanded particles containing the composition (C1) into a mold,

[0180] (ii) The expanded particles containing the thermoplastic elastomer are fused together by supplying energy, at least partially via an electromagnetic field.

[0181] The composition (C1) comprises a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein the composition...

[0182] The compound (C1) has a temperature of 0.3 <JDI M Factor JDI in the range <3 M :

[0183]

[0184] Here, 'i' is an index of the component in the composition.

[0185] Where T m The melting temperature (M) is determined by DSC based on DIN EN ISO 11357-3:2013, measured at a heating rate of 20 K / min and with the sample dried at 100 °C under nitrogen for 10 minutes prior to the start of the measurement, at the maximum enthalpy point at the first peak during the first heating cycle. tanδ is the energy dielectric loss factor of the components of the composition, measured at 80 °C and 27 MHz according to DIN EN IEC 62631-2-2:2022.

[0186] c is the concentration of the component in the composition, expressed as a weight percentage.

[0187] 8. The method according to embodiment 7, wherein the thermoplastic elastomer (TPE1) is thermoplastic polyurethane.

[0188] 9. The method according to any one of embodiments 7 or 8, wherein the thermoplastic polymer (TP1) is selected from the group consisting of polyolefins, polyamides and polystyrene, and particularly from the group consisting of polyethylene and polystyrene.

[0189] 10. The method according to any one of embodiments 7 to 9, wherein the molded body has a tensile strength greater than 0.6 MPa, preferably greater than 0.7 MPa, more preferably greater than 0.8 MPa, more preferably greater than 0.85 MPa, more preferably greater than 0.9 MPa, and especially greater than 1.0 MPa, as determined according to ASTM D 5035:2015.

[0190] 11. The method according to any one of embodiments 7 to 10, wherein in step (ii), a voltage of 3 kV to 9 kV is applied for a duration of 1 second to 300 seconds.

[0191] 12. The method according to any one of embodiments 7 to 11, wherein the molded body has an average thickness in the range of 0.1 cm to 30 cm.

[0192] 13. The method according to any one of embodiments 7 to 12, wherein the thermoplastic elastomer is a thermoplastic polyurethane with a Shore hardness in the range of 70A to 92A.

[0193] 14. The method according to any one of embodiments 7 to 13, wherein in step (i), a crack filling method is used.

[0194] 15. The method according to any one of embodiments 7 to 14, wherein no additives that can be stimulated by an electromagnetic field and cause the temperature in the mold to rise are added in step (i) or (ii).

[0195] 16. Use of expanded particles containing composition (C1) for fusing said particles to prepare a molded body by at least partially supplying energy via an electromagnetic field, wherein said composition (C1) comprises a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein said composition (C1) has a content of 0.3 <JDI M Factor JDI in the range <3 M :

[0196]

[0197] Here, 'i' is an index of the component in the composition.

[0198] Where T m The melting temperature (M) is determined by DSC based on DIN EN ISO 11357-3:2013 at a heating rate of 20 K / min and after drying the sample at 100 °C under nitrogen for 10 minutes prior to the start of the measurement. The maximum enthalpy point at the first peak is determined during the first heating cycle. tanδ is the energy dielectric loss factor of the components of the composition, measured at 80 °C and 27 MHz according to DIN EN IEC 62631-2-2:2022.

[0199] c is the concentration of the component in the composition, expressed as a weight percentage.

[0200] 17. The use according to embodiment 16, wherein the thermoplastic elastomer (TPE1) is a thermoplastic polyurethane.

[0201] 18. The use according to any one of embodiments 16 or 17, wherein the thermoplastic polymer (TP1) is selected from the group consisting of polyolefins, polyamides and polystyrene, and particularly from the group consisting of polyethylene and polystyrene.

[0202] 19. The use according to any one of embodiments 16 to 18, wherein the thermoplastic elastomer is a thermoplastic polyurethane with a Shore hardness in the range of 70A to 92A.

[0203] 20. A molded body that can be obtained by or through the method according to any one of embodiments 7 to 15.

[0204] 21. A molded body, which can be obtained by or by a method for preparing the molded body, the molded body comprising expanded particles containing a composition (C1), the method comprising the following steps:

[0205] (i) Loading the expanded particles containing the composition (C1) into a mold,

[0206] (ii) The expanded particles containing the thermoplastic elastomer are fused together by supplying energy, at least partially via an electromagnetic field.

[0207] The composition (C1) comprises a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein the composition (C1) has a content of 0.3 <JDI M Factor JDI in the range of <3 M :

[0208]

[0209] Here, 'i' is an index of the component in the composition.

[0210] Where T m The melting temperature (M) is determined by DSC based on DIN EN ISO 11357-3:2013, measured at a heating rate of 20 K / min and with the sample dried at 100 °C under nitrogen for 10 minutes prior to the start of the measurement, at the maximum enthalpy point at the first peak during the first heating cycle. tanδ is the energy dielectric loss factor of the components of the composition, measured at 80 °C and 27 MHz according to DIN EN IEC 62631-2-2:2022.

[0211] c is the concentration of the component in the composition, expressed as a weight percentage.

[0212] 22. The molded body according to embodiment 21, wherein the thermoplastic elastomer (TPE1) is thermoplastic polyurethane.

[0213] 23. The molded body according to any one of embodiments 21 or 22, wherein the thermoplastic polymer (TP1) is selected from the group consisting of polyolefins, polyamides and polystyrene, and particularly from the group consisting of polyethylene and polystyrene.

[0214] 24. The molded body according to any one of embodiments 21 to 23, wherein the molded body has a tensile strength greater than 0.6 MPa, preferably greater than 0.7 MPa, more preferably greater than 0.8 MPa, more preferably greater than 0.85 MPa, more preferably greater than 0.9 MPa, and especially greater than 1.0 MPa, as determined according to ASTM D 5035:2015.

[0215] 25. The molded body according to any one of embodiments 21 to 24, wherein in step (ii), a voltage of 3 kV to 9 kV is applied for a duration of 1 second to 300 seconds.

[0216] 26. The molded body according to any one of embodiments 21 to 25, wherein the molded body has an average thickness in the range of 0.1 cm to 30 cm.

[0217] 27. The molded body according to any one of embodiments 21 to 26, wherein the thermoplastic elastomer is a thermoplastic polyurethane with a Shore hardness in the range of 70A to 92A.

[0218] 28. The molded body according to any one of embodiments 21 to 27, wherein in step (i), the crack filling method is used.

[0219] 29. The molded body according to any one of embodiments 21 to 28, wherein no additives that can be stimulated by an electromagnetic field and cause the temperature in the mold to rise are added in step (i) or (ii).

[0220] 39. Use of a molded body according to any one of embodiments 1 to 6, or a molded body obtained by or according to any one of embodiments 7 to 15, in shoe soles, shoe sole parts, shoe midsoles, shoe insoles, shock-absorbing elements, cushioning elements, padding, grips, flooring, mattresses, sporting goods, bicycle saddles, tires, and in motor vehicle interior and exterior parts.

[0221] 40. A molded body comprising expanded particles fused using an electromagnetic field, said expanded particles containing a composition (C1) comprising a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein said composition (C1) has a content of 0.3 <JDI M Factor JDI in the range of <3 M :

[0222]

[0223] Here, 'i' is an index of the component in the composition.

[0224] Where T m The melting temperature (M) is determined by DSC based on DIN EN ISO 11357-3:2013, measured at a heating rate of 20 K / min and with the sample dried at 100 °C under nitrogen for 10 minutes prior to the start of the measurement, at the maximum enthalpy point at the first peak during the first heating cycle. tanδ is the energy dielectric loss factor of the components of the composition, measured at 80 °C and 27 MHz according to DIN EN IEC 62631-2-2:2022.

[0225] c is the concentration of the component in the composition, in weight percentage.

[0226] The thermoplastic elastomer (TPE1) mentioned therein is thermoplastic polyurethane.

[0227] 41. A method for preparing a molded article comprising expanded particles containing composition (C1), the method comprising the following steps

[0228] (i) Loading the expanded particles containing the composition (C1) into a mold,

[0229] (ii) The expanded particles containing the thermoplastic elastomer are fused together by supplying energy, at least partially via an electromagnetic field.

[0230] The composition (C1) comprises a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein the composition (C1) has a content of 0.3 <JDI M Factor JDI in the range of <3 M :

[0231]

[0232] Here, 'i' is an index of the component in the composition.

[0233] Where T m The melting temperature (M) is determined by DSC based on DIN EN ISO 11357-3:2013 at a heating rate of 20 K / min and after drying the sample at 100 °C under nitrogen for 10 minutes prior to the start of the measurement. The maximum enthalpy point at the first peak is determined during the first heating cycle. tanδ is the energy dielectric loss factor of the components of the composition, measured at 80 °C and 27 MHz according to DIN EN IEC 62631-2-2:2022.

[0234] c is the concentration of the component in the composition, in weight percentage.

[0235] This involves achieving fusion using electromagnetic radiation without the use of polar additives.

[0236] 42. A method for preparing a molded article comprising expanded particles containing composition (C1), the method comprising the following steps

[0237] (i) Loading the expanded particles containing the composition (C1) into a mold,

[0238] (ii) The expanded particles containing the thermoplastic elastomer are fused together by supplying energy, at least partially via an electromagnetic field.

[0239] The composition (C1) comprises a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein the composition...

[0240] The compound (C1) has a temperature of 0.3 <JDI M Factor JDI in the range <3 M :

[0241]

[0242] Here, 'i' is an index of the component in the composition.

[0243] Where Tm The melting temperature (M) was determined by DSC based on DIN ENISO 11357-3:2013, with a heating rate of 20 K / min and the sample dried at 100 °C under nitrogen for 10 minutes prior to the start of the measurement, and determined at the maximum enthalpy point at the first peak during the first heating cycle.

[0244] tanδ is the energy dielectric loss factor of the components of the composition, measured at 80°C and 27MHz according to DIN EN IEC 62631-2-2:2022.

[0245] c is the concentration of the component in the composition, in weight percentage.

[0246] In step (i) or (ii), no additives that can be stimulated by an electromagnetic field and cause the temperature in the mold to rise are added.

[0247] 43. The method according to any one of embodiments 41 to 42, wherein the thermoplastic elastomer (TPE1) is thermoplastic polyurethane.

[0248] 44. The method according to any one of embodiments 41 to 43, wherein the thermoplastic polymer (TP1) is selected from the group consisting of polyethylene and polystyrene.

[0249] 45. The method according to any one of embodiments 41 to 44, wherein in step (ii), a voltage of 3 kV to 9 kV is applied for a duration of 1 second to 300 seconds.

[0250] 46. ​​The method according to any one of embodiments 41 to 45, wherein in step (i), a crack filling method is used.

[0251] 47. A molded body that can be obtained by or through the method according to any one of embodiments 41 to 46.

[0252] 48. Use of molded bodies obtained according to or capable of being obtained according to any one of embodiments 41 to 46 in shoe soles, shoe sole parts, shoe midsoles, shoe insoles, shock-absorbing elements, cushioning elements, padding, grips, flooring, mattresses, sporting goods, bicycle saddles, tires, and in motor vehicle interior and exterior parts.

[0253] The invention is further described through embodiments. These embodiments relate to actual and, in some cases, preferred implementations of the invention and do not limit the scope of the invention. Example

[0254] 1. Preparation of Samples and Reference Materials

[0255] 1.1 Materials used

[0256] Blend Partner 1 is commercially available polystyrene (PS 158 K manufactured by BASF SE).

[0257] Blend Partner 2 is a commercially available high molecular weight, high-density polyethylene (Lupolen 4261 AG manufactured by Lyondell Basell).

[0258] Blend Partner 3 is a commercially available polyamide (Ultramid flex F 38 manufactured by BASF SE).

[0259] Blend companion 4 is a commercially available polyamide (Polyamid flex (PA6636) manufactured by BASF SE).

[0260] 1,4BDO 1,4-Butanediol

[0261] 1,6-HDO 1,6-hexanediol

[0262] Xflex 2905 is a bifunctional crosslinking agent.

[0263] 1.2 TPU Synthesis by Extrusion

[0264] The following examples were prepared (see component table 1):

[0265] The production of the examples and references was carried out in a Coperion twin-screw extruder ZSK58 MC with a process length of 48D (12 shells). Melt discharge from the extruder was carried out via a gear pump. After melt filtration, the polymer melt was processed into granules by underwater granulation, which were then continuously dried in a heated vortex bed at 40°C to 90°C.

[0266] The polyol, chain extender, and diisocyanate, along with (if necessary) a catalyst, are metered into the first region. As described above, the additional additives are supplied in region 8.

[0267] Shell temperatures range from 150°C to 230°C. Melt discharge and underwater granulation are carried out at melt temperatures between 210°C and 245°C. Screw speeds are between 180 L / min and 240 L / min. Output ranges from 180 kg / h to 220 kg / h.

[0268] Table 1: Groups of thermoplastic materials metered and added in the reactive extruder as examples and reference (counter-examples) Quantity

[0269]

[0270] 1.4 TPU blends formulated by compounding

[0271] The following blend examples and counterexamples, summarized in Tables 2a and 2b, were prepared in a LabTech LE20-30 single-screw extruder with three to four shells manufactured by LabTech Engineering Company LTD. The polymer melt was processed underwater to receive polymer lines.

[0272] The line is crushed, and the resulting granules are used for injection molding.

[0273] Table 2a: Example and Reference TPU Blends

[0274]

[0275] (*) Comparative Examples

[0276] Table 2b: Example and Reference TPU Blends

[0277] TPU1 4 parts of blend companion <![CDATA[JDI M ]]> Blend 7 95 5 2.81 Blend 8* 85 15 3.64 Blend 9* 70 30 4.89

[0278] (*) Comparative Examples

[0279] 1.5 ETPU extruded

[0280] After the raw materials are produced, they are further processed into expanded thermoplastic polyurethane granules, as described below.

[0281] For this purpose, the dried sample and reference material (see Tables 2a and 2b) were mixed and melted together with additional additives (0.05% to 0.15% by weight of talc as a nucleating agent and possible chain extender (0.6% to 1.2% by weight of polymer composition x-Flex 2905MB, BASF Polyurethanes GmbH) in a twin-screw extruder (ZE40, KraussMaffei Berstorff) at a temperature range of 160°C to 220°C.

[0282] As a blowing agent, CO2 (1.1% to 2.2% by weight based on the polymer composition) and N2 (0.1% to 0.25% by weight based on the polymer composition) are injected into the melt in an extruder and mixed with thermoplastic polyurethane and other additives to form a homogeneous melt.

[0283] The exact polymer compositions of the various embodiments and counterexamples are listed in Tables 1 and 2. The molten mixture was then pumped via a gear pump (approximately 160°C to 200°C, depending on the material composition) into a perforated plate (approximately 180°C to 200°C, depending on the material composition), cut into granules in the cutting chamber of an underwater granulation (UWG) machine, and transported and expanded underwater with conditioned and pressurized water.

[0284] After separating the expanded particles from the water using a centrifugal dryer, the expanded particles were dried at 60°C for 2 hours.

[0285] 2. Molding of eTPU

[0286] Beaded foam was molded using Wave Foamer C from Kurtz at an electromagnetic field frequency of 27.14 MHz (RF molding) and a capacitor plate distance of 4.5 cm. The mold was made of polyethylene terephthalate, with a length and width of 200 mm each, and a variable height that could be set to 10 mm and 20 mm.

[0287] For molding, open the cavity and manually and evenly place the required amount of material (accurately weighed beforehand) into half of the open mold. Then, close the mold to a height of 10mm and begin the molding process. Irradiate the foam beads under a certain voltage for a certain period of time, followed by a cooling step. Finally, reopen the mold and demold the part.

[0288] The amount (by weight) of beaded foam used and the molding conditions are shown in Table 3. This was achieved by adjusting the mold core to 200×200×10mm. 3 The final volume (0.41) of the board is produced. The manufacturing process is carried out as described above. The board is stabilized by waiting time (passive cooling) according to the table below.

[0289] Table 3

[0290]

[0291]

[0292] The examples and comparative examples in Table 3 show that the molded body according to the present invention has a higher tensile strength than the comparative examples.

[0293] Table 4 summarizes other embodiments, which show the parameters JDI. M The impact on the formation of a stable mold.

[0294] Table 4

[0295]

[0296] 3. Method of use

[0297] 3.1 DSC

[0298] DSC measurements were performed based on DIN EN ISO 11357-3:2013 at a heating rate of 20 K / min (the sample was dried at 100 °C under nitrogen for 10 minutes before the measurement began). The melting temperature was determined at the maximum enthalpy point at the first peak during the first heating cycle.

[0299] 3.2 Tensile Strength of E-TPU

[0300] Measurements were performed according to ASTM D 5035:2015, using specimens (150×25mm, 4×10mm; stamped from a plate) at a test rate of 100mm / min.

[0301] 3.3 Component Density

[0302] The density of foamed parts made of thermoplastic polymers is determined based on DIN EN ISO 845:2009.

[0303] 3.4 Dielectric Properties

[0304] The values ​​described in this invention were measured using an impedance analyzer (Keysight E4991B) and a dedicated sample test fixture (16453A), which allows dielectric evaluation from 1 MHz to 1 GHz within a temperature range of -55°C to +150°C according to DIN EN IEC 62631-2-2:2022. The test fixture was placed in a laboratory oven to perform dielectric characterization within the temperature range expected to occur during the molding process. The system was calibrated using open-circuit, short-circuit, and load (with PTFE) compensation prior to measurement.

[0305] References

[0306] WO2014 / 198779 A1

[0307] WO2015 / 052265 A1

[0308] DE102013110242 A1

[0309] EP3698949 A1

[0310] WO2017 / 125410 A1

[0311] WO2017 / 125410 A1

[0312] EP3808522 A1

[0313] WO 2017 / 125410 A1

[0314] WO 2001 / 64414 A1

[0315] WO 2019 / 162172 A1

[0316] DE 10 2013 012 515 A1

[0317] WO 94 / 20568A1

[0318] WO 2007 / 082838 A1

[0319] WO2017 / 030835 A1

[0320] WO 2013 / 153190 A1

[0321] WO 2010 / 010010 A1

[0322] EP3405322A1

[0323] Plastics Handbook, page 7, Polyurethane, Carl Hanser Verlag, page 3, 1993, page 3.1

Claims

1. A molded body comprising expanded particles fused using an electromagnetic field, said expanded particles containing a composition (C1) comprising a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein said composition (C1) has a content of 0.3 <JDI M Factor JDI in the range <3 M : Here, 'i' is an index of the component in the composition. Where T m The melting temperature (M) was determined by DSC based on DIN EN ISO 11357-3:2013, with a heating rate of 20 K / min and the sample dried at 100 °C under nitrogen for 10 minutes before the start of the measurement. It was determined at the maximum enthalpy point at the first peak during the first heating cycle. tanδ is the energy dielectric loss factor of the components of the composition, measured at 80°C and 27MHz according to DIN EN IEC 62631-2-2:2022. c is the concentration of the component in the composition, expressed as a weight percentage.

2. The molded body according to claim 1, wherein the thermoplastic elastomer (TPE1) is thermoplastic polyurethane.

3. A method for preparing a molded article comprising expanded particles containing composition (C1), the method comprising the following steps: (i) Loading the expanded particles containing the composition (C1) into a mold, (ii) The expanded particles containing the thermoplastic elastomer are fused together by supplying energy, at least partially via an electromagnetic field. The composition (C1) comprises a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein the composition (C1) has a content of 0.3 <JDI M Factor JDI in the range of <3 M : Here, 'i' is an index of the component in the composition. Where T m The melting temperature (M) was determined by DSC based on DIN EN ISO 11357-3:2013, with a heating rate of 20 K / min and the sample dried at 100 °C under nitrogen for 10 minutes prior to the start of the measurement. The melting temperature was determined at the maximum enthalpy point at the first peak during the first heating cycle. tanδ is the energy dielectric loss factor of the components of the composition, measured at 80°C and 27MHz according to DIN EN IEC 62631-2-2:2022. c is the concentration of the component in the composition, expressed as a weight percentage.

4. The method of claim 3, wherein fusion by electromagnetic radiation is achieved without the use of polar additives.

5. The method according to claim 3 or 4, wherein no additives that can be stimulated by an electromagnetic field and cause the temperature in the mold to rise are added in step (i) or (ii).

6. The method according to any one of claims 3 to 5, wherein the thermoplastic elastomer (TPE1) is a thermoplastic polyurethane.

7. The method according to any one of claims 3 to 6, wherein the thermoplastic polymer (TP1) is selected from the group consisting of polyethylene and polystyrene.

8. The method according to any one of claims 3 to 7, wherein in step (ii), a voltage of 3 kV to 9 kV is applied for a duration of 1 second to 300 seconds.

9. The method according to any one of claims 3 to 8, wherein in step (i), a crack filling method is used.

10. Use of expanded particles containing composition (C1) for fusing said particles to prepare a molded body by at least partially supplying energy via an electromagnetic field, wherein said composition (C1) comprises a thermoplastic elastomer (TPE1) as component (M) and a thermoplastic polymer (TP1) as component (B1), wherein said composition (C1) has a content of 0.3 <JDI M Factor JDI in the range <3 M : Here, 'i' is an index of the component in the composition. Where T m The melting temperature (M) was determined by DSC based on DIN EN ISO 11357-3:2013, with a heating rate of 20 K / min and the sample dried at 100 °C under nitrogen for 10 minutes prior to the start of the measurement. The melting temperature was determined at the maximum enthalpy point at the first peak during the first heating cycle. tanδ is the energy dielectric loss factor of the components of the composition, measured at 80°C and 27MHz according to DIN EN IEC 62631-2-2:2022. c is the concentration of the component in the composition, expressed as a weight percentage.

11. A molded body that can be obtained by or by any one of claims 3 to 9.

12. Use of the molded body according to claim 1 or 2, or a molded body obtained by or according to any one of claims 3 to 9, in shoe soles, shoe sole parts, shoe midsoles, shoe insoles, shock-absorbing elements, cushioning elements, padding, grips, flooring, mattresses, sporting goods, bicycle saddles, tires, and in motor vehicle interior and exterior parts.

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