New particle foam

Abstract

The present invention relates to a method for producing a thermoplastic polyurethane, comprising at least the steps of converting at least one isocyanate composition (ZI) containing an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4'-diisocyanate (MDI), p-phenyl diisocyanate (PPDI), o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI), or a mixture thereof, and a polyol composition (ZP) containing polytetrahydrofuran or a derivative thereof to obtain a prepolymer having isocyanate groups, and reacting the resulting prepolymer with at least one chain extender (KV). The present invention further relates to a thermoplastic polyurethane obtained or obtainable by such a method, and to a foamed pellet material containing such a thermoplastic polyurethane. The present invention also encompasses a method for using the foamed pellet material of the present invention for the production of a molded article.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a thermoplastic polyurethane, comprising at least the steps of converting at least one isocyanate composition (ZI) containing an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4'-diisocyanate (MDI), p-phenyl diisocyanate (PPDI), o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI), or a mixture thereof, and a polyol composition (ZP) containing polytetrahydrofuran or a derivative thereof to obtain a prepolymer having isocyanate groups, and reacting the resulting prepolymer with at least one chain extender (KV). The present invention further relates to a thermoplastic polyurethane obtained or obtainable by such a method, and to a foamed pellet material containing such a thermoplastic polyurethane. The present invention further encompasses a method for using the foamed pellet material of the present invention to produce a molded article. [Background technology]

[0002] Thermoplastic polyurethanes are known per se. Depending on the desired profile of properties, the isocyanates, polyols, and chain extenders used may vary. Foamed pellet materials, also called bead foams (or particle foams), and molded articles produced therefrom or based on thermoplastic polyurethanes or other elastomers are known per se (e.g., WO 94 / 20568, WO 2007 / 082838, WO 2017030835, WO 2013 / 153190, WO 2010010010) and have a wide range of possible applications. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 94 / 20568 [Patent Document 2] International Publication No. 2007 / 082838 [Patent Document 3] International Publication No. 2017030835 [Patent Document 4] International Publication No. 2013 / 153190 [Patent Document 5] International Publication No. 2010010010 Summary of the Invention [Problem to be solved by the invention]

[0004] For purposes of the present invention, "expanded pellet material" or otherwise "bead foam" or "particle foam" refers to foam in the form of beads, the beads typically having an average diameter of 0.2 to 20 mm, preferably 0.5 to 15 mm, and especially 1 to 12 mm. In the case of non-spherical, e.g., elongated or cylindrical, beads, diameter refers to the longest dimension.

[0005] There is a fundamental need for thermoplastic polyurethanes, especially foamed pellet materials or bead foams, with improved processability to obtain corresponding molded articles at the lowest possible temperatures while maintaining favorable mechanical properties. This is particularly important for the currently widespread fusing methods in which the energy input for fusing the foamed pellets is introduced by an auxiliary medium, such as steam, because improved bonding is achieved here, thus simultaneously reducing damage to the material or foam structure and simultaneously obtaining sufficient bonding or fusing.

[0006] Sufficient bonding or fusion of the foam pellets is essential to obtain favorable mechanical properties of the molded article produced from the foam pellets. If the foam beads are not bonded or fused sufficiently, their properties cannot be fully utilized, resulting in a negative effect on the overall mechanical properties of the resulting molded article. The same considerations apply when there is a weak point in the molded article. In such cases, the mechanical properties will be adversely affected by the weak point, resulting in the same results as above. Therefore, the properties of the polymer used must be efficiently adjustable.

[0007] Known materials often have very low moduli at room temperature, so that for many applications high densities must be achieved to obtain adequate stiffness or stability. At the same time, high resilience and good mechanical properties must be achieved for many applications, and the material must have good weldability in order to produce compacts from the foamed pellet material.

[0008] Within the context of the present invention, "advantageous mechanical properties" should be interpreted with respect to the intended application. The most prominent application for the subject matter of the present invention is in the footwear field, where the expanded pellets can be used in moldings for footwear components where damping and / or cushioning are important, such as insoles and inner soles.

[0009] It is therefore an object of the present invention to provide a thermoplastic polyurethane and foam pellet material based on a thermoplastic polyurethane that is sufficiently rigid but at the same time has good mechanical properties and good processability. It is also an object of the present invention to provide a method for producing the corresponding thermoplastic polyurethane and foam pellet material. [Means for solving the problem]

[0010] The object is, according to the invention, a method for producing a thermoplastic polyurethane, comprising steps (i) and (ii): (i) converting at least one isocyanate composition (ZI) comprising an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4'-diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or a mixture thereof, and a polyol composition (ZP) comprising polytetrahydrofuran or a derivative thereof, to obtain a prepolymer having isocyanate groups; (ii) reacting the prepolymer obtained in step (i) with at least one chain extender (KV) This is achieved by a method comprising at least

[0011] The present invention further relates to a thermoplastic polyurethane obtainable or obtained by the process of the present invention.

[0012] Surprisingly, it has been found that the use of the components used in accordance with the present invention, particularly the specific combination of the isocyanate (IZ) used with a specific polyol component, allows for the production of thermoplastic polyurethanes and foamed pellet materials therefrom that have good processability for forming molded articles, and at the same time have a high modulus and a low softening point, so that the soft phase exhibits a low Tg. Furthermore, the foamed pellet materials of the present invention are characterized by good mechanical properties, such as a high modulus and good resilience. Furthermore, the dynamic retained usability is also very good. Surprisingly, the present invention allows for very good phase separation, with the hard phase simultaneously having better melting ability, resulting in a harder, yet efficiently processable, foamed pellet material. Therefore, it is possible to significantly improve compression hardness compared to conventional materials. Furthermore, the thermoplastic polyurethanes of the present invention and the foamed pellet materials produced therefrom have very good low-temperature properties and good thermal stability.

[0013] Within the context of the present invention, unless otherwise specified, the rebound is determined analogously to DIN 53512 (April 2000); a deviation from the standard is the specimen height, which should be 12 mm, however the test is carried out using 20 mm, unless otherwise specified, to avoid "penetration" of the sample and measurement of the substrate.

[0014] Surprisingly, it has been found that the thermoplastic polyurethanes of the present invention have good processability to give foamed pellet materials which can be further efficiently processed to give molded articles having a particularly high modulus and very good resilience.

[0015] The method of the present invention comprises steps (i) and (ii). In step (i), an isocyanate composition (ZI) containing an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4'-diisocyanate (MDI), p-phenyl diisocyanate (PPDI), o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI), or a mixture thereof, and a polyol composition (ZP) containing polytetrahydrofuran or a derivative thereof are converted to obtain a prepolymer having isocyanate groups. In step (ii), the prepolymer obtained in step (i) is reacted with at least one chain extender (KV). According to the present invention, step (ii) can be carried out after step (i). However, it is also possible to carry out both steps in one step of the method.

[0016] In step (i), the isocyanate composition (ZI) is reacted with a polyol composition (ZP) comprising polytetrahydrofuran or a derivative thereof. According to the present invention, the polyol composition (ZP) comprises at least one polytetrahydrofuran or a derivative thereof and may also comprise further components, in particular further substances reactive with isocyanates, such as further polyols. According to the present invention, the polyol composition may also comprise a mixture of different polytetrahydrofurans having different average molecular weights, or a mixture of polytetrahydrofurans with one or more of its derivatives.

[0017] In a particularly preferred embodiment, the polytetrahydrofuran has a number average molecular weight Mn in the range of 500 g / mol to 5000 g / mol, more preferably in the range of 550 to 2500 g / mol, and especially preferably in the range of 650 to 2000 g / mol.In a further embodiment, the number average molecular weight Mn of the polytetrahydrofuran is in the range of 500 to 1400 g / mol.

[0018] Mixtures of various polytetrahydrofurans, i.e., mixtures of polytetrahydrofurans with different molecular weights, can also be used according to the present invention. According to the present invention, the polyol composition can also further comprise a polyol. Suitable polyols are known to those skilled in the art. Suitable examples are polyethers, polyesters, or polycarbonates.

[0019] In the context of the present invention, polytetrahydrofuran is also referred to as α-hydro-ω-hydroxypoly(oxytetramethylene)diol.

[0020] According to the present invention, the polyol composition comprises polytetrahydrofuran or a derivative thereof. In the context of the present invention, derivative is also understood to mean, for example, a reaction product of polytetrahydrofuran. Suitable derivatives are, for example, those obtained by reaction of the free hydroxyl groups of polytetrahydrofuran. Suitable derivatives are, for example, poly-ε-caprolactone polyols, i.e., polyols obtained by reaction of ε-caprolactone as a starter molecule with polytetrahydrofuran.

[0021] In a further embodiment, the present invention also relates to the method described above, wherein the poly-ε-caprolactone polyol used is obtainable or obtained by reaction of ε-caprolactone and a starter molecule selected from the group consisting of α-hydro-ω-hydroxypoly(oxytetramethylene)diols.

[0022] According to the present invention, the polyol composition may also contain further poly-ε-caprolactone polyols, in particular those having a number-average molecular weight in the range of 500 to 5000 g / mol, preferably in the range of 1000 to 5000 g / mol, and more preferably in the range of 1500 to 2500 g / mol. Preference is given to the use of poly-ε-caprolactone diols, i.e., poly-ε-caprolactone polyols obtained or obtainable using bifunctional starters. Suitable starters in the context of the present invention are, for example, diols having a number-average molecular weight in the range of 80 to 1500 g / mol, such as polyether polyols and polyester polyols. Polyether polyols are particularly suitable.

[0023] Therefore, in a further embodiment, the present invention also relates to the method described above, wherein the poly-ε-caprolactone polyol used is obtainable or obtained by reaction of ε-caprolactone with a starter molecule selected from the group consisting of diols having a number average molecular weight in the range of 50 to 1500 g / mol, preferably in the range of 80 to 2500 g / mol, and even more preferably in the range of 80 to 1500 g / mol.

[0024] Suitable starter molecules are in particular selected from the group consisting of neopentyl glycol (NPG), butane-1,4-diol (BDO), hexane-1,6-diol (HDO) and long-chain polyether diols having a number average molecular weight in the range from 500 to 1500 g / mol, preferably from 800 to 1200 g / mol, more preferably from 900 to 1100 g / mol.

[0025] In the context of the present invention, the number average molecular weight is obtained by determining the OH number, unless otherwise specified. Suitable measurement conditions are known to those skilled in the art.

[0026] In a further embodiment, the present invention also relates to the process described above, wherein the poly-ε-caprolactone polyol used is obtainable or obtained by reacting ε-caprolactone with a starter molecule selected from the group consisting of α-hydro-ω-hydroxypoly(oxytetramethylene)diol, polyethylene glycol and polypropylene glycol, preferably α-hydro-ω-hydroxypoly(oxytetramethylene)diol having a number average molecular weight in the range of 150 to 1500 g / mol, polyethylene glycol having a number average molecular weight in the range of 150 to 1500 g / mol and polypropylene glycol having a number average molecular weight in the range of 150 to 1500 g / mol.

[0027] The polyol composition (ZP) may comprise further α-hydro-ω-hydroxypoly(oxytetramethylene) polyols as further isocyanate-reactive compounds. Suitable α-hydro-ω-hydroxypoly(oxytetramethylene) polyols are known per se. In the context of the present invention, hydro-ω-hydroxypoly(oxytetramethylene) polyols having a number average molecular weight in the range of 1000 to 5000 g / mol, preferably in the range of 1500 to 2500 g / mol, are preferably suitable. In the context of the present invention, it is also possible to use mixtures of two or more hydro-ω-hydroxypoly(oxytetramethylene) polyols having different molecular weights.

[0028] Therefore, in a further embodiment, the present invention also relates to the method as described above, wherein the derivative of polytetrahydrofuran is a poly-ε-caprolactone polyol.

[0029] The composition of the polyol composition (ZP) may vary within wide limits. Preferably, in the context of the present invention, the proportion of α-hydro-ω-hydroxypoly(oxytetramethylene) polyol in the polyol composition (ZP) is in the range of 0.1% to 50% by weight, preferably in the range of 10% to 35% by weight, more preferably in the range of 15% to 25% by weight. In a preferred embodiment, the polyol composition (ZP) consists of a poly-ε-caprolactone polyol and an α-hydro-ω-hydroxypoly(oxytetramethylene) polyol.

[0030] In a further embodiment, the present invention also relates to the above method, wherein the polyol composition comprises α-hydro-ω-hydroxypoly(oxytetramethylene) polyol in an amount of 0.1% to 50% by weight of the polyol composition.

[0031] In a further embodiment, the present invention also relates to the method described above, wherein the poly-ε-caprolactone polyol and / or the α-hydro-ω-hydroxypoly(oxytetramethylene) polyol has a number average molecular weight in the range of 1500 to 2500 g / mol.

[0032] For example, the number average molecular weight of the two polyols in a mixture of poly-ε-caprolactone polyol and α-hydro-ω-hydroxypoly(oxytetramethylene) polyol is about 2000 g / mol.

[0033] Unless otherwise stated, in the context of the present invention, the number average molecular weight Mn is determined by GPC.

[0034] The process of the present invention can also be carried out in such a way that the polyol component (ZP) in the reaction in step (i) contains additional polyols, as well as polytetrahydrofuran and its derivatives. Suitable polyols are generally known 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. Particular preference is given to using polyesterol as polyol (P1) or polyetherol as polyol. It is also possible to use polycarbonate. Copolymers may also be used in the context of the present invention.

[0035] Polyetherols, but also polyesterols, block copolymers and hybrid polyols, such as poly(ester / amides), are suitable according to the invention. Preferred polyetherols according to the invention are polyethylene glycol, polypropylene glycol, polyadipate, polycarbonate, polycarbonate diol and polycaprolactone.

[0036] The polyol compositions used preferably have an average functionality of between 1.8 and 2.3, preferably between 1.9 and 2.2, in particular 2. The polyols used according to the invention preferably have only primary hydroxyl groups.

[0037] According to the present invention, it may be advantageous if water is not used in the reaction in step (i), or in the reaction in step (ii), or in the reaction in step (i) and the reaction in step (ii). Thus, in one embodiment of the present invention, it is possible to use a polyol component that does not contain more than 100 ppm of water.

[0038] According to the present invention, the reaction in step (i) can be carried out at a temperature in the range of, for example, 110 to 180°C, preferably 130 to 170°C, and more preferably 140 to 155°C, to give a prepolymer having an isocyanate group.

[0039] The isocyanate-terminated prepolymers thus obtained according to the invention preferably have an NCO content of 2% to 20% by weight, more preferably 2% to 10% by weight, and especially 2% to 5% by weight. Depending on the NCO content, the resulting prepolymers generally have a viscosity of between 800 and 5000 mPa.s at 80°C, measured using a rotational viscometer.

[0040] Preference is given to producing the isocyanate-terminated prepolymer by using at least 50% by weight, more preferably at least 80% by weight, even more preferably at least 90% by weight, and especially 100% by weight of the polyol component. In the context of the present invention, it is also possible that additional polyols are used in the reaction in step (ii).

[0041] In the context of the present invention, the composition of the polyol composition (PZ) can vary within wide limits. According to the invention, the polyol composition may also contain a solvent. Suitable solvents are known per se to those skilled in the art.

[0042] Therefore, in a further embodiment, the present invention also relates to the method described above, wherein the further component used in the reaction in step (ii) is selected from the group consisting of polyols, chain extenders, catalysts, cell nucleating agents, other auxiliaries and additives.

[0043] In step (i), an isocyanate composition (ZI) is further used. According to the present invention, the isocyanate composition (ZI) comprises an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4'-diisocyanate (MDI), p-phenyl diisocyanate (PPDI), o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI), or a mixture thereof. According to the present invention, the isocyanate composition (ZI) may also comprise a further isocyanate. Preferably, the isocyanate composition (ZI) comprises an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), p-phenyl diisocyanate (PPDI), o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI), or a mixture thereof. More preferably, the isocyanate composition (ZI) comprises naphthylene 1,5-diisocyanate (NDI) as the isocyanate (I1).

[0044] It has been found that thermoplastic polyurethanes with advantageous properties can be obtained, particularly when using naphthylene 1,5-diisocyanate (NDI) or isocyanate mixtures containing naphthylene 1,5-diisocyanate (NDI) and a further isocyanate. According to the invention, it is also possible to use mixtures containing, for example, naphthylene 1,5-diisocyanate (NDI) and diphenylmethane 4,4'-diisocyanate (MDI). Suitable mixtures may contain naphthylene diisocyanate (NDI) and diphenylmethane 4,4'-diisocyanate (MDI) in a ratio ranging from, for example, 50:50 to 30:70.

[0045] Further suitable isocyanates in the context of the present invention are especially diisocyanates, especially aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates.

[0046] Furthermore, within the context of the present invention, a pre-reaction product obtained by reacting a portion of the OH moieties with an isocyanate in a previous reaction step can be used as the isocyanate moiety, which is then reacted with the remaining OH moieties in a subsequent step, the actual polymer reaction, to form the thermoplastic polyurethane.

[0047] If further isocyanates are used, these are preferably present in the isocyanate composition (ZI) in an amount in the range of 0.1% to 20% by weight, more preferably in the range of 0.1% to 10% by weight, and especially preferably in the range of 0.5% to 5% by weight.

[0048] 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.

[0049] Therefore, in a further embodiment, the present invention also relates to the method described above, wherein the polyisocyanate composition comprises an isocyanate selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4'-diisocyanate (MDI), p-phenyl diisocyanate (PPDI), and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI), or a mixture thereof, in an amount ranging from 90% to 100% by weight, based on the total polyisocyanate composition.

[0050] Therefore, in a further embodiment, the present invention also relates to the method described above, wherein the polyisocyanate composition comprises naphthylene 1,5-diisocyanate (NDI) in an amount in the range of 90% to 100% by weight, based on the total polyisocyanate composition.

[0051] In step (ii), the prepolymer obtained in step (i) is reacted with at least one chain extender (KV). If they have not yet been added or have only been partially added in the first step, the prepolymer obtained is preferably reacted in step (ii) with a chain extender (KV), by optionally adding further polyols or further chain extenders, and optionally catalysts, optionally blowing agents and / or crosslinking agents, and optionally auxiliaries and / or additives. In one embodiment of the present invention, the chain extender used contains less than 100 ppm of water.

[0052] According to the invention, the prepolymer obtained in step (i) is preferably reacted in step (ii) in such an amount that the equivalent ratio of NCO groups to the total number of reactive hydrogen atoms is 0.8:1 to 1.5:1, preferably 0.85:1 to 1.3:1, in particular 1.02:1 to 1.15:1. A ratio of 1:1 corresponds to an isocyanate index of 100. In the context of the present invention, isocyanate index is understood to mean the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups multiplied by 100.

[0053] Suitable chain extenders are known to those skilled in the art. Chain extenders are, for example, compounds that have two groups reactive with isocyanate groups, especially 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, preference is given to diols. In the context of the present invention, it is also possible to use a mixture of two or more chain extenders.

[0054] Therefore, in a further embodiment, the present invention also relates to the method described above, wherein the chain extender (KV) is selected from the group consisting of diols having a molecular weight in the range of 50 to 500 g / mol and diamines having a molecular weight in the range of 50 to 500 g / mol.

[0055] According to the present invention, aliphatic, araliphatic, aromatic, and / or cycloaliphatic diols having a molecular weight of 50 g / mol to 220 g / mol can be used as chain extenders. Preference is given to alkanediols having 2 to 10 carbon atoms in the alkylene radical, in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or deca-alkylene glycols. Particular preference is given to MEG, butane-1,4-diol, propane-1,3-diol, and hexane-1,6-diol for the present invention.

[0056] Suitable chain extenders (KV) in the context of the present invention are also branched compounds, such as cyclohexyl-1,4-dimethanol, 2-butyl-2-ethylpropanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol, pinacol, 2-ethylhexane-1,3-diol or cyclohexane-1,4-diol.

[0057] Therefore, in a further embodiment, the present invention also relates to the method described above, wherein the chain extender (KV) is selected from the group consisting of MEG, butane-1,4-diol, propane-1,3-diol, hexane-1,6-diol, 2-ethylhexane-1,3-diol or 2-butyl-2-ethylpropanediol. It is also possible according to the present invention to use a mixture of two or more chain extenders selected from the group consisting of MEG, butane-1,4-diol, propane-1,3-diol, hexane-1,6-diol, 2-ethylhexane-1,3-diol or 2-butyl-2-ethylpropanediol.

[0058] The quantitative ratio of the components used is preferably selected in step (ii) so as to obtain a hard segment content in the range of 10% to 40%.

[0059] According to the present invention, it is possible to carry out the reactions in steps (i) and (ii) in two separate steps. Alternatively, according to the present invention, it is possible to carry out the process in one stage. According to the present invention, the process can be carried out in a multistage or otherwise continuous operation, for example, in a reactive extruder, in which the prepolymer is continuously produced in a first zone. Similarly, it is possible, for example, to first continuously produce the prepolymer according to step (i) in a tubular reactor or tank, and then to carry out step (ii) in the form of a reaction, for example, in a belt extruder or reactive extruder process.

[0060] It has been found to be advantageous, particularly when using an isocyanate composition containing NDI and TODI, to carry out a two-stage process. According to the present invention, it is advantageous to first react a polyol component, an isocyanate component, and optionally an auxiliary or additive, and optionally a catalyst in a first reaction, and then react the resulting prepolymer with a chain extender, optionally an auxiliary or additive, a bubble nucleating agent, and a catalyst. According to the present invention, the NCO / OH ratio is preferably between 0.85 and 1.30.

[0061] A one-step process approach has been found to be advantageous, for example, when using MDI.

[0062] In a further aspect, the present invention also provides a method for producing a compound comprising the steps (i) and (ii): (i) converting at least one isocyanate composition (ZI) comprising an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4'-diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or a mixture thereof, and a polyol composition (ZP) comprising polytetrahydrofuran or a derivative thereof, to obtain a prepolymer having isocyanate groups; (ii) reacting the prepolymer obtained in step (i) with at least one chain extender (KV) The present invention relates to a thermoplastic polyurethane obtainable or obtained by a process comprising at least

[0063] With regard to the preferred embodiment, reference is made to the above remarks relating to preferred starting materials and reaction conditions.

[0064] Surprisingly, it has been found that the thermoplastic polyurethanes of the present invention are particularly suitable for producing foamed pellet materials, the resulting foamed pellets having good mechanical properties, in particular very good resilience.

[0065] The present invention therefore also relates in a further aspect to a thermoplastic polyurethane which can be or is obtainable by the process of the present invention, or to a foamed pellet material comprising the thermoplastic polyurethane of the present invention.

[0066] The foamed pellet material of the present invention has good processability into molded articles. In particular, it has been found that the foamed pellet material has good weldability. In a further aspect, the present invention also relates to molded articles made from the foamed pellet material described above.

[0067] The present invention further relates to the use of a thermoplastic polyurethane obtainable or obtained by the process of the invention or a thermoplastic polyurethane of the invention for the production of moulded articles or foamed pellet materials.

[0068] As with the properties of thermoplastic polyurethanes, the process by which the foamed pellet material is manufactured also often has a decisive effect on the property profile of the resulting beads.

[0069] In a further aspect, the present invention also relates to a method for producing a foamed pellet material, in which case the present invention relates to a method for producing a foamed pellet material, comprising the steps of: (i) at least steps (a) and (b): (a) converting at least one isocyanate composition (ZI) comprising an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4'-diisocyanate (MDI), p-phenyl diisocyanate (PPDI), and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or a mixture thereof, and a polyol composition (ZP) comprising polytetrahydrofuran or a derivative thereof, to obtain a prepolymer having isocyanate groups; (b) reacting the prepolymer obtained in step (a) with at least one chain extender (KV) providing a composition (Z1) comprising a thermoplastic polyurethane obtainable or obtained by a method comprising: (ii) impregnating composition (Z1) with a blowing agent under pressure; (iii) expanding the composition (Z1) by reducing the pressure; The present invention relates to a method, comprising:

[0070] Within the context of the present invention, composition (Z1) can be used here in the form of a melt or in the form of a pellet material.

[0071] For preferred embodiments of the process, suitable starting materials or mixing ratios, reference is made to the correspondingly applicable statements above.

[0072] The method of the present invention may include further steps, such as temperature regulation.

[0073] The unexpanded polymer mixtures of composition (Z1) required for the production of the expanded pellet material are prepared in a known manner from the individual components and, optionally, further components, such as, for example, processing aids, stabilizers, compatibilizers or pigments. Examples of suitable methods are conventional mixing processes with the aid of continuous or batch kneaders or with the aid of extruders, for example co-rotating twin-screw extruders.

[0074] In the case of compatibilizers or auxiliaries, such as stabilizers, they can also be incorporated into the latter during the preparation of the components. The individual components are usually combined before the mixing process or metered into the equipment that performs the mixing. In the case of an extruder, the components are all metered into the inlet and transported together into the extruder, or the individual components are added via side feed.

[0075] Processing occurs at a temperature at which the components are in a plasticized state. The temperature depends on the softening or melting range of the components, but must be lower than the decomposition temperature of each component. Additives such as pigments or fillers, or other of the customary auxiliaries mentioned above, such as flame retardants or antistatic auxiliaries, are also incorporated without melting, but rather in a solid state.

[0076] Further embodiments are possible here, using well-established methods, whereby the processes used in the production of the starting material can be directly integrated into the production. For example, in the case of a belt process, where the material is fed into an extruder to obtain lenticular pellets, it is possible to introduce the polymer, impact modifier, and also fillers or dyes directly at the end of the belt.

[0077] Some of the customary auxiliaries mentioned above may be added to the mixture at this stage.

[0078] The foamed pellet material of the present invention generally has a bulk density of 50 g / l to 200 g / l, preferably 60 g / l to 180 g / l, and more preferably 80 g / l to 150 g / l.

[0079] As specified above, the diameter of the individual beads of the foamed pellets is 0.5 to 30 mm, preferably 1 to 15 mm, in particular 3 to 12 mm. In the case of non-spherical, e.g., elongated or cylindrical, foamed pellets, the diameter refers to the longest dimension.

[0080] The foam pellet material is (i) preparing the composition (Z1) of the present invention; (ii) impregnating the composition with a blowing agent under pressure; (iii) expanding the composition by reducing the pressure; The compounds can be prepared by well-established methods known in the prior art, such as

[0081] The amount of the blowing agent is preferably 0.1 to 50 parts by mass, particularly 0.5 to 35 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of the composition (Z1) used.

[0082] One embodiment of the above method comprises: (i) providing a composition (Z1) of the invention in the form of a pellet material; (ii) impregnating the pellet material with a blowing agent under pressure; (iii) expanding the pellet material by reducing the pressure; Includes.

[0083] A further embodiment of the above method comprises the further step: (i) providing a composition (Z1) of the invention in the form of a pellet material; (ii) impregnating the pellet material with a blowing agent under pressure; (iii-a) reducing the pressure to standard pressure without expanding the pellet material, optionally by first reducing the temperature; (iii-b) expanding the pellet material by increasing the temperature; Includes.

[0084] The unexpanded pellet material herein preferably has an average minimum diameter of 0.2 to 10 mm (determined by 3D evaluation of the pellet material, for example by dynamic image analysis using a PartAn 3D optical measuring instrument from Microtrac).

[0085] In a further embodiment, the present invention also relates to a method for producing the expanded pellet material described above, wherein the polyurethane is impregnated with a blowing agent in an extruder, the impregnated polyurethane is cut into pellet material, and immediately after cutting, the pellet material is expanded to provide expanded thermoplastic polyurethane beads.

[0086] The individual pellets generally have an average mass in the range of 0.1 to 100 mg, for example, in the range of 1 to 50 mg, preferably in the range of 4 to 40 mg, and more preferably in the range of 7 to 32 mg. This average mass of the pellets (bead mass) is determined as the arithmetic mean by weighing three batches of 10 pellet particles each.

[0087] One embodiment of the above-mentioned method comprises steps (I) and (II): (I) Impregnating the pellet material under pressure and at elevated temperature in the presence of a blowing agent in a suitable closed reaction vessel (e.g., an autoclave). (II) A process of rapid expansion without cooling The process involves impregnating pellet material with a blowing agent under pressure, followed by expanding the pellet material.

[0088] The impregnation of step (I) here can be accomplished in the presence of water and, optionally, a suspending agent or suspending aid, or in the presence of only a blowing agent without water.

[0089] Suitable suspending aids include water-insoluble inorganic solids such as tricalcium phosphate, magnesium pyrophosphate, and metal carbonates; polyvinyl alcohol; and ionic surfactants such as sodium dodecylarylsulfonate or nonionic surfactants. They are typically used individually or in combination in amounts of 0.05% to 10% by weight of the composition of the present invention.

[0090] Depending on the pressure chosen, the impregnation temperature ranges from 90°C to 200°C, preferably from 100°C to 200°C, more preferably from 100°C to 180°C, where the pressure in the reactor is between 2 and 250 bar, preferably between 5 and 100 bar, more preferably between 20 and 60 bar, and the impregnation time is generally between 0.5 and 10 hours.

[0091] In a further embodiment, the present invention also relates to a method for producing the above-described expanded pellet material, wherein in step (i) the pellet material is impregnated with 0.1% to 50% by weight of a foaming agent at a temperature in the range of 90 to 180°C and a pressure in the range of 0.5 to 10 MPa.

[0092] The performance of processes in suspension is known to those skilled in the art and is described extensively, for example, in WO 2007 / 082838.

[0093] When the process is run in the absence of a blowing agent, care must be taken to avoid agglomeration of the polymer pellet material.

[0094] Suitable blowing agents for carrying out the process in a suitable closed reaction vessel are, by way of example, organic liquids and gases that are in the gaseous state under the processing conditions, such as hydrocarbons or inorganic gases, or mixtures of organic liquids or gases with inorganic gases, which may also be combined.

[0095] Examples of suitable hydrocarbons are halogenated or non-halogenated, saturated or unsaturated aliphatic hydrocarbons, preferably non-halogenated, saturated or unsaturated aliphatic hydrocarbons.

[0096] Preferred organic blowing agents are saturated aliphatic hydrocarbons, especially those having 3 to 8 carbon atoms, such as butane or pentane.

[0097] Suitable inorganic gases are nitrogen, air, ammonia or carbon dioxide, preferably nitrogen or carbon dioxide, or a mixture of the aforementioned gases.

[0098] In a further embodiment, the impregnation of the pellet material with the blowing agent under pressure comprises the process and subsequent expansion of the pellet material in steps (α) and (β): (α) impregnating pellet material in an extruder under pressure and at elevated temperature in the presence of a blowing agent; (β) pelletizing the composition exiting the extruder under conditions that ensure controlled foaming.

[0099] Suitable blowing agents for this process variant are volatile organic compounds having a boiling point of -25°C to 150°C, especially -10°C to 125°C, at standard pressure (1013 mbar). Suitable are hydrocarbons (preferably halogen-free), especially C4-10-alkanes, such as butane, pentane, hexane, heptane, and octane isomers, more preferably isobutane. Further possible blowing agents are also sterically hindered compounds, such as alcohols, ketones, esters, ethers, and organic carbonates.

[0100] In step (α), the composition is mixed with a blowing agent supplied to the extruder under pressure in a molten state. The blowing agent-containing mixture is extruded under pressure and preferably pelletized (e.g., underwater pelletization) with back pressure controlled to a moderate level. The molten fiber foam in the process and pelletized gives foam pellets.

[0101] The performance of the process via extrusion is known to those skilled in the art and is extensively described, for example, in WO 2007 / 082838 and also in WO 2013 / 153190.

[0102] In one embodiment, for example, polyurethane can be impregnated with a blowing agent in an extruder, the impregnated polyurethane cut into pellets, and the pellets expanded to produce expanded thermoplastic polyurethane beads. To impregnate the polyurethane with the blowing agent, the thermoplastic polyurethane is mixed in the extruder while melted with the blowing agent supplied to the extruder. The blowing agent-containing mixture is then extruded and pelletized under pressure and temperature conditions to produce expanded foam beads. The pressure and temperature depend on the amount of polyurethane and blowing agent used. The pressure is typically in the range of 1 to 20 bar, preferably 2 to 15 bar, and the temperature is between 20°C and 60°C, preferably between 20°C and 40°C.

[0103] The production of thermoplastic polyurethane and the addition of the blowing agent for the production of expanded thermoplastic polyurethane can be achieved in two different extruders. Alternatively, however, it is also possible to use only one extruder. In this case, the front section of the extruder where the isocyanate, isocyanate-reactive compound, chain extender, and any additional additives are added acts as a reactive extruder, and the blowing agent is added downstream of the extruder where the conversion to polyurethane is completed.

[0104] In an alternative embodiment, the production of a foamed pellet material from the thermoplastic polyurethane of the present invention comprises steps (a) to (c): (a) providing a thermoplastic polyurethane in the form of beads of suitable geometric pellet form; (b) impregnating the pellet material with a blowing agent under pressure and temperature in a reservoir or autoclave; (c) allowing the pressure to drop naturally to depressurize the storage tank, causing the foaming agent dissolved in the pellet material to expand and produce foam beads; Includes.

[0105] Generally, the thermoplastic PU is converted into the desired shape of pellets either directly during its production or in a separate step (a). Preference is given to using cylindrical, ellipsoidal or spherical pellets with an average diameter of 0.2 to 10 mm, especially 0.5 to 5 mm. In the case of cylindrical or ellipsoidal pellet material, the diameter of the longest dimension is meant.

[0106] The individual pellets generally have an average mass in the range of 1 to 100 mg, preferably in the range of 2 to 60 mg, even more preferably in the range of 3 to 50 mg, and even more preferably in the range of 4 to 35 mg. This average mass of the pellets (bead mass) is determined as the arithmetic mean by weighing three batches of 10 pellet particles each. This preferably cylindrical or round pellet material can be produced by any compounding method known to those skilled in the art, followed by pelletization in cold or hot chopped form.

[0107] The pellet material is typically impregnated in step (b) in an aqueous suspension containing 0.1% to 50% by weight of a blowing agent at a temperature ranging from 90 to 180°C and a pressure ranging from 0.5 to 10 MPa. The hot aqueous suspension containing the pellet material is then rapidly expanded (explosive expansion method) without cooling using direct expansion of the softened, blowing agent-containing beads to give expanded beads. Expanded thermoplastic polyurethanes can be prepared essentially as described in WO 2007 / 082838.

[0108] The blowing agent used to make the expanded thermoplastic polyurethane beads may vary depending on the manufacturing process.

[0109] When adding the blowing agent to the extruder or impregnation tank, the blowing agent used is preferably a volatile organic compound having a boiling point in the range of -25 to 160°C, especially -10 to 125°C, at a standard pressure of 1013 mbar. Optionally halogen-substituted hydrocarbons are also well suited, with preference given to halogen-free hydrocarbons. C4-C 10Particular preference is given to s-alkanes, such as butane, pentane, cyclopentane, hexane, heptane and octane isomers, more preferably s-pentane.Suitable blowing agents are also sterically more confined compounds, such as alcohols, ketones, esters, ethers and organic carbonates.According to the present invention, it is also possible to use mixtures of the blowing agents mentioned.Suitable inorganic gases are, for example, nitrogen, air, ammonia or carbon dioxide, or combinations thereof or combinations with the above-mentioned additional blowing agents.

[0110] These inorganic gases mentioned above can also be used in the case of impregnation in an autoclave.Halohydrocarbons can also be used, but the blowing agent preferably does not contain halogen.However, a small amount of halogenated blowing agent in the blowing agent mixture is not excluded.The blowing agent can be used as pure substance or any mixture.

[0111] The blowing agents mentioned can likewise be nitrogen and / or carbon dioxide, especially supercritical carbon dioxide, in the case of the production of expanded thermoplastic pellet materials by extrusion and in aqueous suspension.

[0112] The amount of the blowing agent is preferably in the range of 0.1 to 50 parts by mass, particularly 0.5 to 40, and more preferably 1 to 30 parts by mass, based on 100 parts by mass of the thermoplastic polyurethane used.

[0113] Nitrogen may also be supplied as a co-blowing agent by injection and height of internal pressure of 200 to 3000 kPa in the impregnation reactor at a starting temperature below the first melting peak in DSC of the thermoplastic elastomer, for example in the range of 30 to 75°C.

[0114] The impregnation in step (b) is preferably accomplished at an impregnation temperature IMT in the range of 90 to 190° C. For this purpose, the suspension is generally heated to the impregnation temperature (IMT) preferably at a heating rate of 2° C. / min or more and optionally maintained at this temperature or within the range of 2° C. above the IMT to 5° C. below the IMT for 2 to 100 minutes (holding time HZ).

[0115] The blowing agent-containing pellets obtained in step (b) are subsequently expanded into foam beads in step (c). The suspension is expanded in step (c) by transferring the entire pressure vessel into an expansion vessel, typically via an open shut-off valve.

[0116] The foamed pellets made of the thermoplastic polyurethane of the present invention, which can be obtained by the method of the present invention, preferably have a melting point of 20 to 250 kg / m 3 range, more preferably 35 to 150 kg / m 3 It has a bulk density in the range of

[0117] The expanded pellets are generally roughly spherical, with the exact geometry or diameter depending on the geometry selected and the particle mass of the original pelletized material, as well as the resulting bulk density.

[0118] Therefore, the present invention also relates to a foamed pellet material obtainable by the method described above, the particles having an average diameter preferably in the range of 0.5 to 20 mm.

[0119] Typically the particles have a maximum linear expansion in the range of 1 to 25 mm, preferably 2 to 15 mm, more preferably 3 to 10 mm.

[0120] The expanded foam beads produced according to the present invention typically have predominantly closed cells, generally between 1 and 750 cells / mm, as determined by the amount of closed cells according to DIN EN ISO 4590 (August 1, 2003). 2 , preferably 2 to 500 cells / mm 2 , especially 5 to 200 bubbles / mm 2, more preferably 10 to 100 bubbles / mm 2 The foam has a bubble density (number of bubbles / area).

[0121] Equipment suitable for carrying out the process according to the invention for producing expanded beads is known per se to those skilled in the art.

[0122] Extruders that can be used are conventional screw-based machines, in particular single-screw and twin-screw extruders (e.g., ZSK type from Werner & Pfleiderer), co-kneaders, Kombiplast machines, MPC kneading mixers, FCM mixers, KEX kneading screw extruders, and shear roll extruders, as described, for example, in Saechtling (ed.), Kunststoff-Taschenbuch, 27th edition, Hanser-Verlag, Munich 1998, chapters 3.2.1 and 3.2.4. To ensure homogenization of the blowing agent with the melt, the extruder is usually operated at a temperature at which composition (Z1) is present as a melt after the addition of the blowing agent, for example, 120°C to 250°C, in particular 150 to 210°C, and at a pressure of 40 to 200 bar, preferably 60 to 150 bar, more preferably 80 to 120 bar.

[0123] The process herein can be carried out in an extruder or an arrangement consisting of one or more extruders. Thus, for example, in the first extruder, the components can be melted and blended, and a blowing agent can be injected. In the second extruder, the impregnated melt is homogenized and the temperature and / or pressure adjusted. For example, if three extruders are combined, the mixing of the components and the injection of the blowing agent can also be divided between two different process sections. Preferably, if only one extruder is used, all of the process steps—melting, mixing, blowing agent injection, homogenization, and temperature and / or pressure adjustment—are carried out in a single extruder.

[0124] Alternatively, and according to the methods described in WO 2014 / 150122 or WO 2014 / 150124, the corresponding foamed pellets, which may already be coated, can be produced directly from the pellets, which are saturated with a supercritical fluid, removed from the supercritical fluid and subsequently (i') Immersing the article in a heated fluid; or (ii') Irradiating the article with high energy radiation (eg infrared or microwave radiation).

[0125] Examples of suitable supercritical liquids are those described in WO2014150122, i.e., for example, carbon dioxide, nitrogen dioxide, ethane, ethylene, oxygen or nitrogen, preferably carbon dioxide or nitrogen.

[0126] The supercritical fluid here is also 9 MPa -1 / 2 The liquid may include a polar liquid having a Hildebrand solubility parameter greater than or equal to:

[0127] The supercritical fluid or heated fluid herein may also contain a dye, resulting in a colored foamed article.

[0128] Expanded thermoplastic polyurethane beads, i.e., foamed pellet material, are particularly used for the production of molded articles from bead foams. In a further aspect, the present invention also relates to molded articles made from the foamed pellet material described above. The process for producing such molded articles is known per se.

[0129] In a further aspect, the present invention also relates to a method of using the foamed pellet material of the present invention or the foamed pellet material obtained or obtainable by the method of the present invention for the manufacture of a molded article. Thus, in a further embodiment, the present invention also relates to a method of using the foamed pellet material of the present invention or the foamed pellet material obtained or obtainable by the method of the present invention for the manufacture of a molded article, wherein the molded article is manufactured by fusion or bonding of the beads to one another.

[0130] In a further aspect, the present invention also relates to a method of using the foamed pellet material of the present invention for the manufacture of a molded article. The present invention further provides a molded article made from the foamed pellets of the present invention.

[0131] Suitable methods according to the invention for producing moldings from foam pellet material are e.g. (A) introducing the foamed pellets of the present invention into a suitable mold; (B) fusing the foamed pellets of the present invention from step (i); Includes.

[0132] The coalescence in step (B) is preferably achieved in a closed mould and can be achieved by steam, hot air (for example as described in EP 1979401) or high energy radiation (microwave or electromagnetic waves).

[0133] The temperature for the fusion of the foam pellet material is preferably below or close to the melting temperature of the polymer from which the bead foam is made. For standard polymers, the temperature for the fusion of the foam pellet material is therefore between 100°C and 180°C, preferably between 120 and 150°C.

[0134] The temperature profile / residence time can be confirmed here individually, for example in analogy with the methods described in US Patent Application Publication No. 20150337102 or EP Patent No. 2872309.

[0135] Fusion by high-energy radiation is generally achieved in the microwave or electromagnetic frequency range, optionally in the presence of water or other polar liquids, such as microwave-absorbing hydrocarbons with polar groups (e.g., esters of carboxylic acids with diols or triols, or glycols and liquid polyethylene glycols), and can be achieved in analogy to the methods described in EP-A-3053732 or WO-A-16146537.

[0136] A preferred method for the production of individual moldings from such foam beads is (a) introducing expanded thermoplastic polyurethane beads into a mold; (b) contacting the expanded thermoplastic polyurethane beads introduced into the mold with steam, hot air, or high-energy radiation, so that the expanded thermoplastic polyurethane beads melt and weld at the surface to form a molded body; Includes.

[0137] Heating the surface of the foam pellet material beads, which is required for welding to melt at the surface, is achieved by contacting them with steam, hot air, or high-energy radiation, either individually or in any combination. Suitable high-energy radiation is, for example, microwave radiation, high-frequency radiation, or infrared radiation. However, preference is given to using steam or hot air, especially steam.

[0138] Therefore, in a further embodiment, the present invention also relates to the use described above, in which the molded article is produced by welding or bonding the beads together.

[0139] When polyurethane beads are welded using steam, the temperature of the steam introduced into the mold can be adjusted via the pressure. According to the invention, it is also possible to use saturated steam as well as superheated or unsaturated steam. Suitable pressures at which the steam is introduced into the mold are, for example, 0.1 bar to 6 bar, preferably 0.3 to 3 bar.

[0140] As noted above, the foam pellet material may also include a dye, where the dye can be added in a variety of ways.

[0141] In one embodiment, the foamed pellets produced can be colored after production by contacting the corresponding foamed pellets with a dye-containing carrier liquid (CL) with a polarity suitable for sorption of the carrier liquid (CL) into the foamed pellet material. This can be carried out similarly to the method described in European Patent Application No. 17198591.4.

[0142] Examples of suitable pigments are inorganic or organic pigments. Examples of suitable natural or synthetic inorganic pigments are carbon black, graphite, titanium oxide, iron oxide, zirconium oxide, cobalt oxide compounds, chromium oxide compounds, and copper oxide compounds. Examples of suitable organic pigments are azo pigments and polycyclic pigments.

[0143] In a further embodiment, the colorant can be added during the production of the foam pellet material. For example, the pigment can be added to the extruder during the production of the foam pellet material via extrusion.

[0144] Alternatively, already colored material can be used as the starting material for the production of foamed pellet material, which can be extruded or expanded in a closed container by the processes listed above.

[0145] Furthermore, in the method described in WO2014150122, the supercritical fluid or heated liquid may comprise a dye.

[0146] As clearly indicated above, the moulded articles of the invention have advantageous properties for the above mentioned applications in the requirements of the footwear and sports shoe sector.

[0147] Characteristic features of the tensile and compressive properties of moulded articles made from the expanded pellets are a tensile strength of more than 600 kPa (ASTM D 5035), an elongation at break of more than 100% (ASTM D 503), and a compressive stress at 10% compression of more than 15 kPa (analogous to DIN EN ISO 844 (November 2014); deviations from the standard are a sample height of 20 mm instead of 50 mm, and therefore an adjusted test speed of 2 mm / min).

[0148] The resilience of the moldings made from the foam pellets is preferably greater than 55% (similar to DIN 53512 (April 2000); the deviation from the standard is the specimen height, which should be 12 mm, but the test is carried out using 20 mm to avoid "piercing" the sample and measuring the substrate).

[0149] As stated above, there is a relationship between the density and compressibility of the produced moldings. The density of the produced moldings is advantageously between 75 and 375 kg / m 3 , preferably 100 to 300 kg / m 3 , more preferably 150 to 200 kg / m 3 (DIN EN ISO 845 (October 2009)).

[0150] The ratio of the density of the molding to the bulk density of the foamed pellets according to the invention (densification level VG) is generally between 1.5 and 3.5, preferably between 1.8 and 2.5.

[0151] The foamed pellets of the present invention can be processed with particular efficiency to provide footwear soles, footwear sole parts, mattresses, underlayments, grips, protective membranes, automotive interior and exterior components, gymnastics mats, personal protective equipment, maintenance elements for automotive structures, sound insulation, vibration dampers, cushions, bicycle saddles, toys, tires or tire parts, or covers for track and field surfaces, sports halls or walkways, damping layers or cores of sandwich elements, or packaging.

[0152] Therefore, in a further embodiment, the present invention also relates to a method of use as described above, wherein the molded article is a footwear sole, a part of a footwear sole, a mattress, an underlay, a grip, a protective membrane, a component of an automobile interior and exterior, a gymnastics mat, personal protective equipment, a maintenance element of an automobile structure, a sound insulator, a vibration damper, a cushion, a bicycle seat, a toy, a tire or tire part, or a cover for a track and field surface, a sports hall or a walkway, a damping layer or core of a sandwich element, or a packaging.

[0153] In a further aspect, the present invention also relates to the use of the foamed pellet material described above in balls and sports equipment or as floor coverings and wall panels, in particular as floor coverings and wall panels for sports surfaces, track and field surfaces, sports halls, children's playgrounds and walkways.

[0154] The molded articles obtainable according to the invention are suitable, for example, in the manufacture of footwear soles, parts of footwear soles, bicycle saddles, cushions, mattresses, underlays, grips, protective membranes, components for automobile interiors and exteriors, in balls and sports equipment, or as floor coverings and wall panels, in particular for sports surfaces, track and field surfaces, sports halls, children's playgrounds and walkways.

[0155] Therefore, in a further embodiment, the present invention also relates to the use of the foamed pellet material of the present invention or of the foamed pellet material obtained or obtainable by the method of the present invention for the manufacture of molded articles, wherein the molded articles are shoe soles, parts of shoe soles, bicycle saddles, cushions, mattresses, underlays, grips, protective membranes, components for automobile interior and exterior surfaces.

[0156] In a further aspect, the present invention also relates to the use of the foam pellets or foam beads of the present invention in balls and sports equipment or as floor coverings and wall panels, in particular as floor coverings and wall panels for sports surfaces, track and field surfaces, sports halls, playgrounds and walkways.

[0157] In a further aspect, the present invention also relates to a hybrid material comprising a polymer matrix (PM) and a foamed pellet material according to the present invention. A material comprising a foamed pellet material and a matrix material is referred to as a hybrid material in the context of the present invention. The matrix material here may be composed of a dense material or a similar foam.

[0158] Polymers (PM) suitable as matrix materials are known to those skilled in the art. For example, ethylene vinyl acetate copolymers, epoxy binders, or other polyurethanes are suitable in the context of the present invention. Polyurethane foams or other high-density polyurethanes, such as thermoplastic polyurethanes, are also suitable in the present invention.

[0159] According to the invention, the polymer (PM) is now chosen so that there is sufficient adhesion between the foamed pellet material and the matrix, resulting in a mechanically stable hybrid material.

[0160] The matrix here can completely or partially surround the foamed pellet material. According to the present invention, the hybrid material may also contain further components, for example, further fillers or other pellets. According to the present invention, the hybrid material may also contain a mixture of different polymers (PM). The hybrid material may also contain a mixture of foamed pellets.

[0161] In addition to the foam pellet material according to the invention, foam pellets that can be used are known per se to those skilled in the art. Foam pellets made of thermoplastic polyurethane are particularly suitable in the context of the present invention.

[0162] Therefore, in one embodiment, the present invention also relates to a hybrid material comprising a matrix made of a polymer (PM), a foamed pellet material according to the invention and a further foamed pellet material made of a thermoplastic polyurethane.

[0163] In the context of the present invention, the matrix consists of a polymer (PM). Examples of suitable matrix materials in the context of the present invention are elastomers or foams, in particular foams based on elastomers such as polyurethanes, for example ethylene vinyl acetate copolymers or other thermoplastic polyurethanes.

[0164] Therefore, the present invention also relates to the hybrid material described above, in which the polymer (PM) is an elastomer.The present invention further relates to the hybrid material described above, in which the polymer (PM) is selected from the group consisting of ethylene vinyl acetate copolymers and thermoplastic polyurethanes.

[0165] In one embodiment, the present invention also relates to a hybrid material comprising a matrix composed of ethylene vinyl acetate copolymer and a foamed pellet material according to the present invention.

[0166] In a further embodiment, the present invention relates to a hybrid material comprising a matrix made of ethylene vinyl acetate copolymer, a foamed pellet material according to the present invention and a further foamed pellet material made of, for example, a thermoplastic polyurethane.

[0167] In one embodiment, the present invention relates to a hybrid material comprising a matrix composed of a thermoplastic polyurethane and an expanded pellet material according to the present invention.

[0168] In a further embodiment, the present invention relates to a hybrid material comprising a matrix made of thermoplastic polyurethane, a foamed pellet material according to the present invention and a further foamed pellet material, for example made of thermoplastic polyurethane.

[0169] Suitable thermoplastic polyurethanes are known per se to those skilled in the art and are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd Edition 1993, Chapter 3.

[0170] In the context of the present invention, the polymer (PM) is preferably polyurethane. "Polyurethane" within the meaning of the present invention encompasses all known resilient polyurethane polyaddition products. These include, in particular, polyaddition products such as dense polyurethanes, viscoelastic gels, or thermoplastic polyurethanes, as well as resilient foams based on polyisocyanate polyaddition products, such as flexible foams, semi-rigid foams, or integrated foams. Within the meaning of the present invention, "polyurethane" is also understood to mean resilient polymer blends comprising polyurethanes and additional polymers, as well as foams of these polymer blends. The matrix is ​​preferably a cured dense polyurethane binder, a resilient polyurethane foam, or a viscoelastic gel.

[0171] Within the context of the present invention, "polyurethane binder" is understood here to mean a mixture of prepolymers containing isocyanate groups to an extent of at least 50% by weight, preferably at least 80% by weight, and in particular at least 95% by weight, hereinafter referred to as isocyanate prepolymers. The viscosity of the polyurethane binders of the present invention, measured at 25°C to DIN 53 018, is preferably in the range of 500 to 4000 mPa.s, more preferably 1000 to 3000 mPa.s.

[0172] In the context of the present invention, "polyurethane foam" should be understood to mean foam according to DIN 7726.

[0173] The density of the matrix material is preferably 1.2 to 0.01 g / cm 3 The matrix material is preferably a resilient foam or a material having a density of 0.8 to 0.1 g / cm 3 , especially 0.6 to 0.3 g / cm 3 or a denser material such as a cured polyurethane binder.

[0174] Foam is a particularly suitable matrix material. Hybrid materials that include a matrix material composed of polyurethane foam preferably have good adhesion between the matrix material and the foam pellet material.

[0175] In one embodiment, the present invention also relates to a hybrid material comprising a matrix composed of polyurethane foam and a foam pellet material according to the present invention.

[0176] In a further embodiment, the present invention relates to a hybrid material comprising a matrix made of polyurethane foam, a foamed pellet material according to the present invention and a further foamed pellet material made of, for example, a thermoplastic polyurethane.

[0177] In one embodiment, the present invention relates to a hybrid material comprising a matrix composed of an integral foam of polyurethane and a foam pellet material according to the present invention.

[0178] In a further embodiment, the present invention relates to a hybrid material comprising a matrix made of an integral foam of polyurethane, a foamed pellet material according to the present invention and a further foamed pellet material made of, for example, a thermoplastic polyurethane.

[0179] The hybrid material of the present invention comprising a polymer (PM) as a matrix and the expanded pellet material of the present invention can be produced, for example, by mixing the components used to produce the polymer (PM) with the expanded pellet material, and optionally further components, and reacting them to give the hybrid material, the reaction being preferably achieved under conditions under which the expanded pellet material is essentially stable.

[0180] Suitable processes and reaction conditions for producing polymers (PM), in particular ethylene vinyl acetate copolymers or polyurethanes, are known per se to those skilled in the art.

[0181] In a preferred embodiment, the hybrid material of the present invention is an integral foam, especially an integral foam based on polyurethane. Processes suitable for producing integral foams are known to those skilled in the art. The integral foam is preferably produced by a one-shot process using low-pressure or high-pressure techniques in a closed, advantageously temperature-controlled mold. The mold is usually made of metal, such as aluminum or steel. These procedures are described, for example, by Piechota and Roehr in "Integralschaumstoff" [Integral Foam], Carl-Hanser-Verlag, Munich, Vienna, 1975, or in "Kunststoff-Handbuch", Vol. 7, "Polyurethane", 3rd Edition, 1993, Chapter 7.

[0182] When the hybrid material of the present invention contains an integral foam, the amount of the reaction mixture introduced into the mold is such that the resulting molded article made of the integral foam has a density of 0.08 to 0.70 g / cm. 3 , especially 0.12 to 0.60 g / cm 3 The densification level for producing moldings with dense edge zones and cellular cores is in the range of 1.1 to 8.5, preferably 2.1 to 7.0.

[0183] Therefore, it is possible to manufacture a hybrid material incorporating the foamed pellet material of the present invention, which has a matrix composed of a polymer (PM) and in which the foamed beads are uniformly distributed. The foamed pellet material of the present invention is free-flowing due to the small size of the individual beads, and does not require special processing requirements, so it can be easily used in the process of manufacturing a hybrid material. Here, it is possible to use techniques such as slowly rotating the mold to uniformly distribute the foamed pellet material.

[0184] Further auxiliaries and / or additives may also optionally be added to the reaction mixture for producing the hybrid material of the present invention. As examples, mention may be made of surface-active substances, foam stabilizers, cell regulators, mold release agents, fillers, dyes, pigments, hydrolysis stabilizers, odor-absorbing substances and fungistatic and bacteriostatic substances.

[0185] The example of surface-active substance that can be used is the compound that is suitable for supporting the homogenization of starting material, and optionally also for adjusting foam structure.Example of emulsifier that can be mentioned is for example castor oil sulfate or sodium salt of fatty acid, and also the salt of fatty acid with amine, for example, diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate, salt of sulfonic acid, for example, alkali metal salt or ammonium salt of dodecylbenzene or dinaphthylmethane disulfonic acid and ricinoleic acid; foam stabilizer, for example, siloxane-oxyalkylene copolymer and other organopolysiloxane, ethoxylated alkylphenol, ethoxylated fatty alcohol, paraffin oil, castor oil ester or ricinoleic acid ester, turmeric oil and peanut oil, and foam regulator, for example, paraffin, fatty alcohol, dimethylpolysiloxane. Oligomeric acrylates having polyoxyalkylene and fluoroalkane radicals as pendant groups are also suitable for improving the emulsification, cell structure and / or foam stabilization.

[0186] Suitable release agents include, for example, reaction products of fatty acid esters with polyisocyanates, salts of fatty acids with amino-containing polysiloxanes, salts of saturated or unsaturated (cyclo)aliphatic carboxylic acids having at least 8 carbon atoms with tertiary amines, and also, in particular, internal release agents, such as mixtures of montanic acid and at least one aliphatic carboxylic acid having at least 10 carbon atoms with at least difunctional alkanolamines, polyols and / or polyamines having a molecular weight of 60 to 400, organic amines, mixtures of metal salts of stearic acid with organic mono- and / or dicarboxylic acids or their anhydrides, or carboxylic acid esters and / or carboxylic acid amides prepared by esterification or amidation of mixtures of imino compounds, carboxylic acids and, optionally, metal salts of carboxylic acids.

[0187] Fillers, especially reinforcing fillers, are understood to mean conventional organic and inorganic reinforcing fillers, extenders, agents for improving the wear behavior of paints, coating compositions, and the like, which are known per se. Specific examples that may be mentioned are: inorganic fillers such as siliceous minerals, for example, layered silicates, such as antigorite, bentonite, serpentine, hornblende, amphibole, chrysotile, and talc; metal oxides, such as kaolin, aluminum oxide, titanium oxide, zinc oxide, and iron oxide; metal salts, such as chalk and barite; and inorganic pigments, such as cadmium sulfide and zinc sulfide, and also glass. Preference is given to the use of natural and synthetic fibrous minerals, such as kaolin (china clay), aluminum silicate, and coprecipitates of barium sulfate and aluminum silicate, and also wollastonite; metal fibers; and, in particular, glass fibers of various lengths, which may be of any size. Examples of useful organic fillers include: carbon black, melamine, rosin, cyclopentadienyl resins and graft polymers, and also cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters, and especially carbon fibers.

[0188] The inorganic and organic fillers can be used individually or as a mixture.

[0189] In the hybrid material of the present invention, the volume fraction of the foamed pellet material is preferably 20 volume percent or more, more preferably 50 volume percent or more, more preferably 80 volume percent or more, and especially 90 volume percent or more, based in each case on the volume of the hybrid system of the present invention.

[0190] The hybrid materials of the present invention, particularly those having a matrix composed of cellular polyurethane, feature excellent adhesion of the matrix material to the foamed pellet material of the present invention. As a result, the hybrid materials of the present invention preferably do not tear at the interface between the matrix material and the foamed pellet material. This allows the production of hybrid materials with improved mechanical properties, such as tear propagation resistance and elastic modulus, compared to conventional polymer materials, particularly conventional polyurethane materials, at the same density.

[0191] The modulus of elasticity of the hybrid material of the invention in the form of an integral foam is preferably greater than 40% according to DIN 53512, more preferably greater than 50%.

[0192] Furthermore, the hybrid material of the present invention, especially that based on the integral foam, has low density and high resilience.The integral foam based on the hybrid material of the present invention is therefore particularly suitable as a material for shoe soles.As a result, lightweight and comfortable soles with good durability are obtained.Such materials are particularly suitable as insoles for sports shoes.

[0193] The hybrid material of the present invention having a cellular matrix is ​​suitable for example for cushions, for example for furniture and mattresses.

[0194] Hybrid materials with a matrix composed of viscoelastic gels are particularly characterized by enhanced viscoelasticity and improved elasticity, and are thus also suitable, for example, as cushioning materials for seating, especially for saddles, such as bicycle or motorcycle saddles.

[0195] Hybrid materials with a dense matrix are suitable, for example, as floor coverings, in particular as coverings for playgrounds, track and field surfaces, playgrounds and sports halls.

[0196] The properties of the hybrid materials of the present invention may vary within wide limits depending on the polymer (PM) used, and in particular by the addition of further additives, for example also further non-expanded pellets such as plastic pellets, for example rubber pellets, by varying the size, shape and properties etc. of the expanded pellet material.

[0197] The hybrid materials of the present invention have high durability and toughness, which is manifested in particular by high tensile strength and elongation at break. Additionally, the hybrid materials of the present invention have low density.

[0198] Further embodiments of the present invention can be found in the claims and examples. It will be recognized that the features of the subject matter / method / use according to the present invention listed above and clarified below can be used not only in the combinations explicitly stated in each case, but also in other combinations without departing from the scope of the present invention. For example, combinations of preferred features with particularly preferred features, or combinations of features not further characterized with particularly preferred features, etc. are therefore implicitly encompassed, even if the combination is not explicitly recited. DETAILED DESCRIPTION OF THE INVENTION

[0199] Illustrative embodiments of the present invention are listed below, but these do not limit the present invention. In particular, the present invention also encompasses the embodiments resulting from the dependent references and therefore the combinations specified below.

[0200] 1. A method for producing a thermoplastic polyurethane, comprising steps (i) and (ii): (i) converting at least one isocyanate composition (ZI) comprising an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4'-diisocyanate (MDI), p-phenyl diisocyanate (PPDI), and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or a mixture thereof, and a polyol composition (ZP) comprising polytetrahydrofuran or a derivative thereof, to obtain a prepolymer having isocyanate groups; (ii) reacting the prepolymer obtained in step (i) with at least one chain extender (KV) The method includes at least

[0201] 2. The method of embodiment 1, wherein the derivative of polytetrahydrofuran is a poly-ε-caprolactone polyol.

[0202] 3. The method of embodiment 1 or 2, wherein the further component used in the reaction in step (ii) is selected from the group consisting of polyols, chain extenders, catalysts, cell nucleating agents, other auxiliaries and additives.

[0203] 4. The method according to any one of the preceding claims, wherein the poly-ε-caprolactone polyol is obtainable or obtained by reaction of ε-caprolactone with a starter molecule selected from the group consisting of polytetrahydrofurans having a number average molecular weight ranging from 500 to 2500 g / mol.

[0204] 5. The method according to any one of the preceding claims, wherein the poly-ε-caprolactone polyol is obtainable or obtainable by reaction of ε-caprolactone with a starter molecule selected from the group consisting of α-hydro-ω-hydroxypoly(oxytetramethylene)diols.

[0205] 6. The method of any one of the preceding claims, wherein the polyol composition comprises α-hydro-ω-hydroxypoly(oxytetramethylene) polyol in an amount ranging from 0.1% to 50% by weight of the polyol composition.

[0206] 7. The method of any one of the preceding claims, wherein the polyisocyanate composition comprises naphthylene 1,5-diisocyanate (NDI) in an amount ranging from 90% to 100% by weight, based on the total polyisocyanate composition.

[0207] 8. The method of any one of the preceding claims, wherein the chain extender (KV) is selected from the group consisting of diols having a molecular weight in the range of 50 to 500 g / mol and diamines having a molecular weight in the range of 50 to 500 g / mol.

[0208] 9. The method of any one of the preceding claims, wherein the chain extender (KV) is selected from the group consisting of MEG, butane-1,4-diol, propane-1,3-diol, hexane-1,6-diol, 2-ethylhexane-1,3-diol or 2-butyl-2-ethylpropanediol.

[0209] 10. Steps (i) and (ii): (i) converting at least one isocyanate composition (ZI) comprising an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4'-diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or a mixture thereof, and a polyol composition (ZP) comprising polytetrahydrofuran or a derivative thereof, to obtain a prepolymer having isocyanate groups; (ii) reacting the prepolymer obtained in step (i) with at least one chain extender (KV) 1. A thermoplastic polyurethane obtainable or obtained by a process comprising at least

[0210] 11. The thermoplastic polyurethane according to embodiment 10, wherein the derivative of polytetrahydrofuran is a poly-ε-caprolactone polyol.

[0211] 12. The thermoplastic polyurethane of embodiment 10 or 11, wherein the further component used in the reaction in step (ii) is selected from the group consisting of polyols, chain extenders, catalysts, cell nucleating agents, other auxiliaries and additives.

[0212] 13. The thermoplastic polyurethane according to any one of embodiments 10 to 12, wherein the poly-ε-caprolactone polyol is obtainable or obtained by reacting ε-caprolactone with a starter molecule selected from the group consisting of polytetrahydrofurans having a number average molecular weight in the range of 500 to 2500 g / mol.

[0213] 14. The thermoplastic polyurethane according to any one of embodiments 10 to 13, wherein the poly-ε-caprolactone polyol is obtainable or obtained by reacting ε-caprolactone with a starter molecule selected from the group consisting of α-hydro-ω-hydroxypoly(oxytetramethylene)diols.

[0214] 15. The thermoplastic polyurethane of any one of embodiments 10 to 14, wherein the polyol composition comprises α-hydro-ω-hydroxypoly(oxytetramethylene) polyol in an amount ranging from 0.1% to 50% by weight, based on the polyol composition.

[0215] 16. The thermoplastic polyurethane of any one of embodiments 10 to 15, wherein the polyisocyanate composition comprises naphthylene 1,5-diisocyanate (NDI) in an amount ranging from 90% to 100% by weight, based on the total polyisocyanate composition.

[0216] 17. The thermoplastic polyurethane of any one of embodiments 10 to 16, wherein the chain extender (KV) is selected from the group consisting of diols having a molecular weight in the range of 50 to 500 g / mol and diamines having a molecular weight in the range of 50 to 500 g / mol.

[0217] 18. The thermoplastic polyurethane of any one of embodiments 10 to 17, wherein the chain extender (KV) is selected from the group consisting of MEG, butane-1,4-diol, propane-1,3-diol, hexane-1,6-diol, 2-ethylhexane-1,3-diol, or 2-butyl-2-ethylpropanediol.

[0218] 19. A foamed pellet material comprising a thermoplastic polyurethane obtainable or obtained by the method of any one of embodiments 1 to 9, or a thermoplastic polyurethane according to any one of embodiments 10 to 18.

[0219] 20. Use of a thermoplastic polyurethane obtainable or obtained by the method according to any one of embodiments 1 to 9 or according to any one of embodiments 10 to 18 for the manufacture of a molded article or a bead foam.

[0220] 21. A method for producing a foamed pellet material comprising thermoplastic polyurethane according to any one of claims 10 to 18, wherein the polyurethane is impregnated with a foaming agent in an extruder, the impregnated polyurethane is cut into pellet material, and the pellet material is expanded immediately after cutting to provide expanded thermoplastic polyurethane beads.

[0221] 22. A method for producing a foamed pellet material comprising the thermoplastic polyurethane according to any one of embodiments 10 to 18, comprising steps (a) to (c): (a) providing a thermoplastic polyurethane in the form of beads of suitable geometric pellet form; (b) impregnating the pellet material with a blowing agent under pressure and temperature in a reservoir or autoclave; (c) allowing the reservoir to naturally depressurize by reducing the pressure, thereby expanding the foaming agent dissolved in the pellet material and producing foam beads; A method comprising:

[0222] 23. The method of embodiment 22, wherein the pellet material in step (b) is impregnated with 0.1% to 50% by weight of a blowing agent at a temperature in the range of 90 to 180°C and a pressure in the range of 0.5 to 10 MPa.

[0223] 24. A foamed pellet material obtainable by the method according to any one of embodiments 21 to 23.

[0224] 25. The foamed pellet material of embodiment 24, wherein the beads have an average diameter in the range of 0.5 to 20 mm.

[0225] 26. A molded article obtainable from the foamed pellet material according to embodiment 24 or 25.

[0226] 27. A method for producing a molded article from the foamed pellet material of embodiment 24 or 25, comprising steps (a) and (b): (a) introducing the expanded thermoplastic polyurethane beads into a mold; (b) contacting the expanded thermoplastic polyurethane beads introduced into the mold with steam, hot air, or high-energy radiation, so that the expanded thermoplastic polyurethane beads melt and weld at the surface to form a molded body. A method comprising:

[0227] 28. The foamed pellet material of embodiment 19, wherein the beads have an average diameter in the range of 0.5 to 20 mm.

[0228] 29. A molded article obtainable from the foamed pellet material according to embodiment 19 or 28.

[0229] 30. Use of the foam bead material according to embodiment 19 or 28 for the production of molded articles.

[0230] 31. The method of use according to embodiment 30, wherein the shaped article is produced by fusing or bonding beads together.

[0231] 32. Method of use according to embodiment 30 or 31, wherein the molded article is a footwear sole, a part of a footwear sole, a mattress, an underlay, a grip, a protective membrane, a component of an automobile interior or exterior, a gymnastics mat, a personal protective equipment, a maintenance element of an automobile structure, a sound insulation material, a vibration damper, a cushion, a bicycle seat, a toy, a tire or tire part, or a cover for a track and field surface, a sports hall or walkway, a damping layer or core of a sandwich element, or a packaging.

[0232] 33. Use of the foamed pellet material according to embodiment 19 or 28 in balls and sports equipment or as floor coverings and wall panels, in particular for sports surfaces, track and field surfaces, sports halls, playgrounds and walkways.

[0233] 34. A hybrid material comprising a matrix composed of a polymer (PM) and the expanded pellet material according to embodiment 19 or 28.

[0234] 35. A method for producing a thermoplastic polyurethane, comprising steps (i) and (ii): (i) a step of converting at least one isocyanate composition (ZI) containing an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), p-phenyl diisocyanate (PPDI), o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or a mixture thereof, and a polyol composition (ZP) containing polytetrahydrofuran or a derivative thereof, to obtain a prepolymer having isocyanate groups; (ii) reacting the prepolymer obtained in step (i) with at least one chain extender (KV) The method includes at least

[0235] 36. The method of claim 35, wherein the derivative of polytetrahydrofuran is a poly-ε-caprolactone polyol.

[0236] 37. The method of claim 35 or 36, wherein the further component used in the reaction in step (ii) is selected from the group consisting of polyols, chain extenders, catalysts, bubble nucleating agents, other auxiliaries and additives.

[0237] 38. The method according to any one of claims 35 to 37, wherein the poly-ε-caprolactone polyol is obtainable or obtained by reaction of ε-caprolactone with a starter molecule selected from the group consisting of α-hydro-ω-hydroxypoly(oxytetramethylene)diols.

[0238] 39. The method of any one of claims 35 to 38, wherein the polyisocyanate composition comprises naphthylene 1,5-diisocyanate (NDI) in an amount ranging from 90% to 100% by weight based on the total polyisocyanate composition.

[0239] 40. The method according to any one of claims 35 to 39, wherein the chain extender (KV) is selected from the group consisting of diols having a molecular weight in the range of 50 to 500 g / mol and diamines having a molecular weight in the range of 50 to 500 g / mol.

[0240] 41. The method of any one of claims 35 to 40, wherein the chain extender (KV) is selected from the group consisting of MEG, butane-1,4-diol, propane-1,3-diol, hexane-1,6-diol, 2-ethylhexane-1,3-diol or 2-butyl-2-ethylpropanediol.

[0241] 42. Steps (i) and (ii): (i) converting at least one isocyanate composition (ZI) comprising an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), p-phenyl diisocyanate (PPDI) and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or a mixture thereof, and a polyol composition (ZP) comprising polytetrahydrofuran or a derivative thereof, to obtain a prepolymer having isocyanate groups; (ii) reacting the prepolymer obtained in step (i) with at least one chain extender (KV) 1. A thermoplastic polyurethane obtainable or obtained by a process comprising at least

[0242] 43. A foamed pellet material comprising a thermoplastic polyurethane obtainable or obtained by a method according to any one of claims 35 to 41, or a thermoplastic polyurethane according to claim 42.

[0243] 44. The foamed pellet material of claim 43, wherein the beads have an average diameter in the range of 0.5 to 20 mm.

[0244] 45. A molded article obtainable from the expanded bead material according to claim 43 or claim 44.

[0245] 46. ​​Use of the foam bead material according to claim 43 or 44 for the production of molded articles.

[0246] 47. Use according to claim 46, in which the shaped article is produced by fusing or bonding beads together.

[0247] 48. Use according to claim 46 or 47, wherein the molded article is a footwear sole, a part of a footwear sole, a mattress, an underlay, a grip, a protective membrane, a component of an automobile interior or exterior, a gymnastics mat, personal protective equipment, a maintenance element of an automobile structure, a sound insulator, a vibration damper, a cushion, a bicycle seat, a toy, a tire or tire part, or a cover for a track and field surface, a sports hall or walkway, a damping layer or core of a sandwich element, or packaging.

[0248] 49. Use of the foamed pellet material according to claim 43 or 44 in balls and sports equipment or as floor coverings and wall panels, in particular as floor coverings and wall panels for sports surfaces, track and field surfaces, sports halls, children's playgrounds and walkways.

[0249] 50. A hybrid material comprising a matrix composed of a polymer (PM) and the foamed pellet material according to claim 43 or 44.

[0250] 51. A method for producing a thermoplastic polyurethane, comprising steps (i) and (ii): (i) a step of converting at least one isocyanate composition (ZI) containing naphthylene diisocyanate (NDI) as the isocyanate (I1) and a polyol composition (ZP) containing polytetrahydrofuran or a derivative thereof to obtain a prepolymer having isocyanate groups; (ii) reacting the prepolymer obtained in step (i) with at least one chain extender (KV) The method includes at least

[0251] 52. The method of claim 51, wherein the derivative of polytetrahydrofuran is a poly-ε-caprolactone polyol.

[0252] 53. The method of claim 51 or 52, wherein the further component used in the reaction in step (ii) is selected from the group consisting of polyols, chain extenders, catalysts, bubble nucleating agents, other auxiliaries and additives.

[0253] 54. The method according to any one of claims 51 to 53, wherein the poly-ε-caprolactone polyol is obtainable or obtained by reaction of ε-caprolactone with a starter molecule selected from the group consisting of α-hydro-ω-hydroxypoly(oxytetramethylene)diols.

[0254] 55. The method of any one of claims 51 to 54, wherein the polyisocyanate composition comprises naphthylene 1,5-diisocyanate (NDI) in an amount ranging from 90% to 100% by weight based on the total polyisocyanate composition.

[0255] 56. The method according to any one of claims 51 to 55, wherein the chain extender (KV) is selected from the group consisting of diols having a molecular weight in the range of 50 to 500 g / mol and diamines having a molecular weight in the range of 50 to 500 g / mol.

[0256] 57. The method of any one of claims 51 to 56, wherein the chain extender (KV) is selected from the group consisting of MEG, butane-1,4-diol, propane-1,3-diol, hexane-1,6-diol, 2-ethylhexane-1,3-diol or 2-butyl-2-ethylpropanediol.

[0257] 58. Steps (i) and (ii): (i) a step of converting at least one isocyanate composition (ZI) containing naphthylene diisocyanate (NDI) as the isocyanate (I1) and a polyol composition (ZP) containing polytetrahydrofuran or a derivative thereof to obtain a prepolymer having isocyanate groups; (ii) reacting the prepolymer obtained in step (i) with at least one chain extender (KV) 1. A thermoplastic polyurethane obtainable or obtained by a process comprising at least

[0258] 59. A foamed pellet material comprising a thermoplastic polyurethane obtainable or obtained by a method according to any one of claims 51 to 57, or a thermoplastic polyurethane according to claim 58.

[0259] 60. The foamed pellet material of claim 59, wherein the beads have an average diameter in the range of 0.5 to 20 mm.

[0260] 61. A molded article obtainable from the foam pellet material according to claim 59 or 60.

[0261] 62. Use of the foamed pellet material according to claim 59 or 60 for the production of molded articles.

[0262] 63. Use according to claim 62, in which the shaped article is produced by fusing or bonding beads together.

[0263] 64. Use according to claim 62 or 63, wherein the molded article is a footwear sole, a part of a footwear sole, a mattress, an underlay, a grip, a protective membrane, a component of an automobile interior or exterior, a gymnastics mat, personal protective equipment, a maintenance element of an automobile structure, a sound insulator, a vibration damper, a cushion, a bicycle seat, a toy, a tire or tire part, or a cover for a track and field surface, a sports hall or walkway, a damping layer or core of a sandwich element, or packaging.

[0264] 65. Use of the foamed pellet material according to claim 59 or 60 in balls and sports equipment or as floor coverings and wall panels, in particular as floor coverings and wall panels for sports surfaces, track and field surfaces, sports halls, children's playgrounds and walkways.

[0265] 66. A hybrid material comprising a matrix composed of a polymer (PM) and the foamed pellet material of claim 59 or 60.

[0266] The examples which follow serve to illustrate the invention but in no way limit it with respect to its subject matter. [Example]

[0267] 1. Example of the production of thermoplastic polyurethane 1.1 Experiment 1 (TPU 1) 1000 parts by weight of polyol (PTHF capped with PCL (PCL500-PTHF1000-PCL500), PTHF2000 4:1) was heated to a temperature between 130 and 160 °C, and 200 parts by weight of NDI was added in solid form and allowed to react. After a reaction time of 30 to 50 minutes in the temperature range of 150 to 90 °C, a prepolymer with an NCO content of 3.2% and a viscosity of 2500 mPa.s was obtained at 90 °C.

[0268] Within 2 hours after production, 100 parts by weight of the prepolymer thus obtained were homogeneously mixed with 3.4 parts by weight of butane-1,4-diol at a temperature of 90°C and introduced into a mold having a mold temperature between 80 and 100°C.

[0269] After a curing time of 20-30 minutes, the material was subjected to a heat treatment at a temperature of 110°C for 14 hours. The resulting material can be further processed by injection molding.

[0270] The resulting TPU 1 was pelletized by milling and converted into lenticular granules via submerged pelletization by extrusion using a ZSK40 twin-screw extruder with a maximum zone temperature of 220° C. and a perforated plate temperature of 230° C. The TPU was then dried at 80° C. for 15 hours.

[0271] 1.2 Experiment 2 (TPU 2) 1000 parts by weight of polyol (PTHF capped with PCL, PTHF2000 4:1) were heated to a temperature between 130 and 160°C, and 200 parts by weight of NDI in solid form were added and reacted. After a reaction time of 30 to 50 minutes in the temperature range of 150 to 90°C, a prepolymer with an NCO content of 2.87% and a viscosity of 2960 mPa.s was obtained at 90°C.

[0272] Within 4 hours after production, 100 parts by weight of the prepolymer thus obtained were homogeneously mixed with 2.73 parts by weight of a mixture consisting of 100 parts of propane-1,3-diol and 5 parts of an amine catalyst mixture (65% N-methyl-N-dimethylaminoethylpiperazine and 35% pentamethyldiethylenetriamine) at a temperature of 90°C and introduced into a mold having a mold temperature between 80 and 100°C.

[0273] After a curing time of 20-30 minutes, the material is subjected to a heat treatment at a temperature of 110° C. for 14 hours, and the resulting material can be further processed by injection molding.

[0274] In a subsequent reprocessing to give lenticular granules, talc was added at a concentration of 0.05%.

[0275] 1.3 Method for determining NCO content: solution: Di-n-hexylamine solution: Homogenize 166.8 g of di-n-hexylamine with xylene up to 1.0 L (in a 1 L gauge flask).

[0276] 1% Bromophenol Blue Solution: Dissolve 0.5 g of bromophenol blue in 49.5 g of ethanol and transfer to a pipette bottle.

[0277] procedure: Dispense 10 mL of the amine solution into an Erlenmeyer flask. Then, add 20 mL of chlorobenzene. Weigh out 2 g to 2.5 g of prepolymer to the nearest 0.1 mg for an expected isocyanate content of 4% (the mass for other isocyanate concentrations must be adjusted accordingly). After complete dissolution (visual check), add 50 mL of methanol. After adding three drops of bromophenol blue solution, back-titrate the unconsumed amine with HCl (c = 1.0 mol / L) until the color changes from blue to yellow.

[0278] A blank sample, ie, a sample containing no prepolymer, was treated in the same manner except that the sample was not weighed.

[0279] Calculation: Free NCO=(((V BLK -V 試料 )* M * c * t ) / m)* 100% [In the formula, V BLK = HCl consumed in 1 L of blank (1.0 mol / L) V 試料 = HCl consumed in 1 L of sample (1.0 mol / L) M = molar mass of NCO 42.02 g / mol Molar concentration of C=HCl 1.9 mol / L t=HCl titer (1.0mol / L) m = mass of prepolymer sample in 1 g

[0280] 1.4 Example 3 (TPU 3) - Reactive Extruder a. Example of sequential synthesis NDI and optional solid additives are fed into the first barrel of a ZSK32 MC twin-screw extruder from Coperion with a processing length of 56D. A polyol heated to 160°C, as well as a catalyst and optional liquid additives, are fed to the molten NDI in the second barrel. After the components are mixed and (partially) reacted, a chain extender is added downstream in the fifth zone. At a barrel temperature of 190-220°C, the reaction components are converted to a conversion level of over 95%. After synthesis, the resulting polymer melt is subjected to submerged pelletization, and the resulting pellets are dried.

[0281] As a variation of the method specified above, all of the liquid ingredients can be added to Zone 2.

[0282] [Table 1]

[0283] [Table 2]

[0284] 2. Test method: Test methods / indexes used to characterize the pellet materials used and the resulting foam beads and molded articles include:

[0285] a. Melting point measurement by DSC Procedure of ISO 11357-3 (German edition of 04.01.2013) using a DSC Q100 from TA Instruments. To determine the melting point of the thermoplastic elastomer used, or other thermoplastic elastomers of the present invention, 3-5 mg in pellet form is heated between 20°C and 200°C at a heating rate of 20°C / min in a first run, then cooled to 20°C at 10°C / min, followed by a further heating cycle (second run) at a heating rate of 10°C / min. The melting point reported was the peak maximum temperature in the second run.

[0286] b. Bulk density The measurement was carried out in accordance with DIN EN ISO 60:2000-1, whereby the foam beads are introduced with the aid of a fixed-shape funnel into a measuring cylinder of known volume (completely filled with bulk material), the bulk material protruding from the measuring cylinder is levelled with a straight-edged rod and the content of the measuring cylinder is determined by weighing.

[0287] The funnel used was 40 cm high, with an opening angle of 35° and an outlet diameter of 50 mm. The measuring cylinder used had an internal diameter of 188 mm and a capacity of 10 L.

[0288] Material [kg] / 0.01[m 3 The bulk density (SD) was calculated from the mass of the layer.

[0289] Reported bulk densities are in kg / m 3 The results were the average of three measurements.

[0290] c. Average cell density The foam structure was evaluated by visual image analysis using a PORE!SCAN Advanced Plus from Goldlücke Ingenieurleistungen. For this purpose, in each case, 10 foam beads were divided into two equal halves and the cross-sectional area was measured. In the case of non-spherical, e.g., elongated, cylindrical, or ellipsoidal, foam beads, the division was along the longest dimension.

[0291] The average bubble density is the ratio of the number of bubbles in a cross-sectional area to the cross-sectional area, and is 1 / mm 2 Report at.

[0292] Assign values ​​to the following categories: Classification Average bubble density [1 / mm 2 ] F Fine bubbles >100 N Normal bubbles 10~100 G Coarse bubbles <10

[0293] d. Densification level VG The densification level VG is the ratio of compact density (FT density) to bulk density (SD). VG = FT density [kg / m 3 ] / SD[kg / m 3 ].

[0294] e. Further testing methods: Additionally, test methods used for material characterization may include: DMA, TMA, NMR, FT-IR, GPC Apparent density DIN EN ISO 845:2009-10 Tear propagation resistance DIN EN ISO 8067:2009-06 Dimensional stability ISO 2796:1986-08 Tensile Test ASTM D5035:2011 Elasticity DIN 53512:2000-4

[0295] 3. Preparation of foam beads by impregnation in an autoclave 3.1 Starting materials For E-TPU Examples 1 to 7 (and the Comparative Example), the following TPU materials were used: Density (20kg / m 3 ) TPU in the form of lenticular pellets 1 1150kg / m 3 TPU 2 in the form of lenticular pellets 1150kg / m 3

[0296] Experiments were carried out using a reservoir fill level of 80% and a phase ratio of 0.38, where phase ratio is defined as the ratio between the amount of pellets and the suspension medium, which in the examples is water.

[0297] 3.2 General Manufacturing Methods (e.g., E-TPU Example 1 to E-TPU Example 7) 100 parts by weight of pellets (corresponding to 27.1% by weight of the entire suspension without blowing agent), 262 parts by weight of water (corresponding to 71.0% by weight of the entire suspension without blowing agent), 6.7 parts by weight of calcium carbonate (suspension aid) (corresponding to 1.8% by weight of the entire suspension without blowing agent), 0.13 parts by weight of a surfactant (Lutensol AT 25; suspension aid) (corresponding to 0.04% by weight of the entire suspension without blowing agent), and an appropriate amount of butane as a blowing agent (relative to the amount of pellets used) were heated with stirring.

[0298] Nitrogen was then injected into the liquid phase at a further 50°C. The internal pressure was adjusted to a predetermined pressure (800 kPa). Following this, when the impregnation temperature (IMT) was reached, and optionally after observing a holding time (HZ), the mixture was finally expanded through an expansion device at the established impregnation pressure (IMP). Here, the gas space was adjusted to a fixed discharge pressure (AP) and kept constant during the expansion. The expanded jet downstream of the expansion device may optionally be cooled at a specific temperature (water quench) with a specific volumetric flow rate of water.

[0299] The holding time is defined as the time during which the temperature of the liquid phase is in the temperature range of 5°C below the impregnation temperature and 2°C above the impregnation temperature.

[0300] After removal of the suspension medium / suspending aid system (dispersant / surfactant) and drying, the bulk density (SD) of the resulting foam beads is measured.

[0301] Tables 1a and 1b list the exact manufacturing parameters and bulk densities of the resulting batches (foam beads).

[0302] [Table 3]

[0303] [Table 4]

[0304] 4. Manufacturing of compacts The foam beads (expanded pellets) were subsequently welded in a molding machine from Kurtz Ersa GmbH (Energy Foamer K68) to obtain square plaques with a side length of 200 mm and a thickness of 10 mm and 20 mm by contacting them with steam, or in a molding machine from Erlenbach (EHV-C870 / 670) to obtain rectangular plaques with a side length of 300 x 200 mm and a thickness of 10 mm.

[0305] The compacts can be produced by either the pressure injection method or the crack injection method. For the inventive examples, the crack injection method was used (see Table 2).

[0306] After production, the compacts were stored at 60°C to 70°C for 4 to 16 hours, and then the compact densities were tested (Table 2).

[0307] [Table 5]

[0308] Table 3 lists the results of the type tests.

[0309] [Table 6]

[0310] 5. Examples of Hybrid Material Fabrication 5.1 General manufacturing procedure for hybrid materials The beads prepared above were used to produce moldings using a PU system or binder. For this purpose, a liquid formulation was first prepared, then the beads were vigorously mixed in a plastic container made of polyethylene, and then released into a mold. The mold used was a Teflon-coated wooden mold with internal dimensions of 4.5 x 4.5 x 4.5 cm. It was possible to produce either cubes or slabs 2 cm thick from the formulation using a 4.5 x 4.5 x 2.5 cm inlay.

[0311] 5.2 Starting Materials Beads used: E-TPU1 5.3 Foaming Systems and Binders Ingredient A 94 copies

[0312] [Table 7]

[0313] Component B 100 parts of Iso137 / 28 (NCO[%] 18.00)

[0314] [Table 8]

[0315] 5.4 Gel systems Ingredient A 100 copies

[0316] [Table 9]

[0317] Component B 11 parts

[0318] [Table 10]

[0319] 5.5 Results

[0320] [Table 11]

[0321] 6. Fabrication of eTPU / PU foam hybrid sheets With the help of a dosing machine (4K TPY NDF 20-4 low pressure machine from Elastogran GmbH), component A preheated to 40°C and component B preheated to 25°C, together with the compositions listed in Table 4, were added to the appropriate amount of E-TPU in a 2.7 L plastic beaker at a pressure of 16 bar with time control according to the details from Table 4.

[0322] [Table 12]

[0323] The dosage parameters are derived from the fact that approximately 10% of the total mass of the foaming system remains lost during mixing and transfer of the E-TPU and foam. This is 300 kg / m 3 (PU foam 1) or 260 kg / m 3 This is checked by weighing the finished test sheet, adjusted to the density of (PU foam 2).

[0324] [Table 13]

[0325] Immediately thereafter, the components and E-TPU were immediately mixed for a maximum of 10 seconds with the aid of a laboratory stirrer (model EWTHV-05 from Vollrath GmbH) and then introduced into open aluminum molds with dimensions of 20 x 20 x 1 cm or 20 x 20 x 2 cm, preheated to 45°C and coated with silicone (marbo super release s), and distributed homogeneously until a gelation time of approximately 40 seconds was reached. The aluminum molds were heated using an SC 100 heating device from Thermo Scientific.

[0326] After closing the mold, the system is allowed to react to completion for 30 minutes, during which the ventilation of the mold is controlled by a ventilation channel while maintaining a constant mold temperature at 45°C.

[0327] Before testing the test sheets, they were stored at room temperature for at least two days to ensure that the PU foam had reacted to completion. The resilience (also called rebound) according to DIN 53512: 2000-04 and density according to DIN EN ISO 845: 2009-10 of the resulting 20 mm sheets are listed in the table.

[0328] [Table 14]

[0329] PU Foam 3 was processed using the same procedure as Foams 1 and 2, with a low level of catalyst, and a 70% bead mass fraction was introduced. PU Foam 4, due to its faster reaction time, was introduced directly into the E-TPU-filled mold, around which the foam was subsequently formed. A fully filled mold allows for a bead mass fraction of approximately 50%. The faster reaction system achieves a demold time of approximately 5 minutes. All other processing parameters were maintained.

[0330] The following mechanical test data was determined on a 20 mm thick test sheet.

[0331] [Table 15]

[0332] References: WO 94 / 20568 A1 WO 2007 / 082838 A1 WO 2017 / 030835 A1 WO 2013 / 153190 A1 WO 2010 / 010010 A1 “Kunststoffhandbuch”, volume 7, “Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapter 3.1 Saechtling (ed.), Kunststoff-Taschenbuch, 27th edition, Hanser-Verlag Munich 1998, chapters 3.2.1 and 3.2.4 WO 2014 / 150122 A1 WO 2014 / 150124 A1 EP 1979401B1 US 20150337102 A1 EP 2872309B1 EP 3053732 A WO 2016 / 146537 A1 “Plastics Handbook”, volume 7, “Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapter 3 "Integralschaumstoff" (Integral Foam), Carl-Hanser-Verlag, Munich, Vienna, 1975, or in Kunststoff-Handbuch (Plastics Handbook), volume 7, Polyurethane, 3rd edition, 1993, chapter 7

Claims

1. Steps (i) and (ii): (i) converting at least one isocyanate composition (ZI) containing an isocyanate (I1) selected from the group consisting of naphthylene 1,5-diisocyanate (NDI), diphenylmethane 4,4′-diisocyanate (MDI), p-phenyl diisocyanate (PPDI), o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) and mixtures thereof, and a polyol composition (ZP) containing a poly-ε-caprolactone polyol, which is a derivative of polytetrahydrofuran, to obtain a prepolymer having isocyanate groups; (ii) reacting the prepolymer obtained in step (i) with at least one chain extender (KV); A foamed pellet material comprising a thermoplastic polyurethane obtained by a process comprising at least the steps of:

2. 2. The foamed pellet material of claim 1, wherein the further components used in the reaction in step (ii) are selected from the group consisting of polyols, chain extenders, catalysts, bubble nucleating agents, other auxiliaries and additives.

3. 3. The foamed pellet material according to claim 1 or 2, wherein the poly-ε-caprolactone polyol is obtained by reaction of ε-caprolactone with a starter molecule selected from the group consisting of α-hydro-ω-hydroxypoly(oxytetramethylene)diols.

4. The at least one isocyanate composition (ZI) comprises naphthylene 1,5-diisocyanate (NDI) in an amount ranging from 90% to 100% by weight based on the total amount of the at least one isocyanate composition (ZI). The foamed pellet material according to any one of claims 1 to 3.

5. The foamed pellet material according to any one of claims 1 to 4, wherein the at least one chain extender (KV) is selected from the group consisting of diols having a molecular weight in the range of 50 to 500 g / mol and diamines having a molecular weight in the range of 50 to 500 g / mol.

6. 6. The foamed pellet material of any one of claims 1 to 5, wherein the at least one chain extender (KV) is selected from the group consisting of MEG, butane-1,4-diol, propane-1,3-diol, hexane-1,6-diol, 2-ethylhexane-1,3-diol, and 2-butyl-2-ethylpropanediol.

7. The foamed pellet material according to any one of claims 1 to 6, wherein the average diameter of the beads of the foamed pellet material is in the range of 0.5 to 20 mm.

8. A molded article obtained from the foamed pellet material according to any one of claims 1 to 7.

9. 8. Use of the foamed pellet material according to any one of claims 1 to 7 for the production of moulded articles.

10. 10. The method of use according to claim 9, wherein the moulded article is produced by fusing or bonding beads of the foamed pellet material together.

11. 11. The method of use according to claim 9 or 10, wherein the molded article is a footwear sole, a part of a footwear sole, a mattress, an underlay, a grip, a protective membrane, a component of an automobile interior and exterior, a gymnastics mat, a personal protective equipment, a maintenance element of an automobile structure, a sound insulation material, a vibration damper, a cushion, a bicycle seat, a toy, a tire or a tire part, or a cover of a track and field surface, a sports hall or a passageway, a damping layer or a damping core of a sandwich element, or a packaging.

12. 8. Use of the foamed pellet material according to any one of claims 1 to 7 in balls and sports equipment or as floor coverings and wall panels.

13. A hybrid material comprising a matrix composed of a polymer (PM) and the foamed pellet material according to any one of claims 1 to 7.

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