Glass fiber-reinforced TPU

Abstract

To provide a composition containing a reinforced thermoplastic polyurethane having good mechanical properties, good low-temperature properties and high rigidity.SOLUTION: A composition comprising: a thermoplastic polyurethane (TPU-1) which is obtained or can be obtained by the reaction of a polyisocyanate composition (IZ) with a polyol composition (PZ); and a filler (F1), wherein the polyol composition (PZ) comprises at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2). It also relates to a process for the production of the composition, to the use of the composition according to the invention for the production of moulded bodies and also to moulded bodies comprising the composition according to the invention.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition comprising a thermoplastic polyurethane (TPU-1) obtained or obtainable by reacting a polyisocyanate composition (IZ) with a polyol composition (PZ), and a filler (F1), wherein the polyol composition (PZ) comprises at least one polyol (P1), a chain extender (KV1), and a chain extender (KV2). The present invention also relates to a method for producing the composition. Furthermore, the present invention relates to the use of the composition according to the invention for producing a molded body, and also to a molded body comprising the composition according to the invention. [Background technology]

[0002] Glass fiber reinforced thermoplastic polyurethane is known as a high-performance material that combines excellent mechanical properties with a very low coefficient of thermal expansion. This material can withstand high stresses and is used in a variety of applications.

[0003] Good glass fiber reinforced thermoplastic polyurethanes can be made from MDI-based thermoplastic polyurethanes, for example. The MDI-based hard phase provides very good mechanical properties.

[0004] Also of interest are glass-fiber-reinforced TPUs based on polyethers, which have very high impact toughness, especially at low temperatures. These materials are used in various functional components of sports equipment, such as ski boots and skis.

[0005] However, some applications require very stiff materials with E moduli greater than 10,000 MPa, but producing suitable materials is very difficult, firstly because a very stiff TPU starting material is required, and secondly because a very high degree of glass fiber loading must be achieved. Summary of the Invention [Problem to be solved by the invention]

[0006] It is therefore an object of the present invention to provide a reinforced thermoplastic polyurethane having high stiffness, which should further have good mechanical properties, good low temperature properties and be easily processable. [Means for solving the problem]

[0007] According to the invention, the object is to (a) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of a polyisocyanate composition (IZ) with a polyol composition (PZ), the polyol composition (PZ) comprising at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), and (b) Filler (F1) This is achieved by a composition comprising: DETAILED DESCRIPTION OF THE INVENTION

[0008] Surprisingly, it has been found that the inventive combination of thermoplastic polyurethane and filler used results in compositions with improved property profiles. Thus, the melting range of the very hard TPU can be optimized by first using a specific polyol composition according to the present invention. It has been found that the addition of a second chain extender in the synthesis of the very hard TPU results in a starting material capable of producing glass fiber reinforced TPUs with E moduli exceeding 10,000 MPa.

[0009] The composition according to the present invention comprises at least one filler (F1) and a thermoplastic polyurethane (TPU-1). In the context of the present invention, the thermoplastic polyurethane (TPU-1) is obtained or can be obtained by reacting a polyisocyanate composition (IZ) with a polyol composition (PZ), wherein the polyol composition (PZ) comprises at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2).

[0010] Thermoplastic polyurethanes are known per se. They are produced by reacting isocyanates, isocyanate-reactive compounds, and chain extenders, optionally in the presence of at least one catalyst and / or conventional auxiliaries and / or additives. The isocyanates, isocyanate-reactive compounds, and chain extenders, individually or jointly, are also referred to as formative components.

[0011] According to the present invention, a thermoplastic polyurethane (TPU-1) can be obtained by reacting a polyisocyanate composition (IZ) with a polyol composition (PZ). The polyol composition (PZ) comprises at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2). For the purposes of the present invention, the polyol composition can also comprise additional polyols.

[0012] As chain extenders (KV1) and (KV2), it is possible to use commonly known aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds, preferably bifunctional compounds, having a molecular weight, preferably an average molecular weight, of 50 g / mol to 499 g / mol. Preference is given to alkanediols having 2 to 10 carbon atoms in the alkylene radical, preferably 1,4-butanediol, 1,6-hexanediol, and / or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or deca-alkylene glycols having 3 to 8 carbon atoms, more preferably unbranched alkanediols, in particular 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol.

[0013] Therefore, in a further embodiment, the present invention also provides a composition as described above, wherein the chain extender (KV1) and / or the chain extender (KV2) is selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol, diethylene glycol, triethylene glycol, hydroquinone bis-2-hydroxyethyl ether and bis(2-hydroxyethyl) terephthalate.

[0014] In the context of the present invention, more preferably, the chain extender (KV1) is selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. Thus, in a further embodiment, the present invention also provides a composition as described above, wherein the chain extender (KV1) is 1,4-butanediol.

[0015] In the context of the present invention, preferably 1,3-propanediol or 1,6-hexanediol is used as chain extender (KV2), more preferably 1,3-propanediol is used as chain extender (KV2). Thus, in a further embodiment, the present invention provides a thermoplastic polyurethane as described above, wherein the chain extender (KV2) is 1,3-propanediol.

[0016] According to the present invention, it is also possible to use polyhydric alcohols, such as propanediol, and / or further diols, which are at least partially obtained from renewable raw materials. In this case, the polyhydric alcohols can be obtained partly or entirely from renewable raw materials. According to the present invention, at least one of the polyhydric alcohols used can be obtained at least partly from renewable raw materials.

[0017] What is known as bio-1,3-propanediol can be obtained, for example, from corn and / or sugar. The conversion of glycerol waste from biodiesel production is also possible. In a further preferred embodiment of the present invention, the polyhydric alcohol is 1,3-propanediol obtained at least in part from renewable raw materials.

[0018] Therefore, in a further embodiment, the present invention provides a composition as described above, wherein the thermoplastic polyurethane is based on renewable raw materials to an extent of at least 30%. A suitable method for determining is, for example, the C14 method.

[0019] The mixing ratio of the chain extenders (KV1) and (KV2) used can vary within a wide range. Preferably, the chain extenders (KV1) and (KV2) are used in a ratio ranging from 75:25 to 99:1.

[0020] According to the present invention, additional chain extenders may also be used in the polyol composition.

[0021] According to the present invention, the polyol composition (PZ) comprises at least a polyol (P1) as an isocyanate-reactive compound. For the purposes of the present invention, in principle, all polyols suitable in themselves can be used, such as polyesterols, polyetherols, and / or polycarbonate diols. For example, the polyols used can have a molecular weight (Mn) in the range of 500 g / mol to 8000 g / mol and preferably have an average functionality with respect to isocyanates of 1.8 to 2.3, preferably 1.9 to 2.2, in particular 2. Unless otherwise specified, the number average molecular weight is determined in accordance with DIN 55672-1.

[0022] The polyol (P1) used preferably has a molecular weight in the range of 600 to 2000 daltons, more preferably in the range of 750 to 1500 daltons, in particular a molecular weight of about 1000 daltons.

[0023] The polyesterol can be a polyester based on a diacid and a diol. As the diol, preferably a diol having 2 to 10 carbon atoms, such as ethanediol, butanediol, or hexanediol, in particular 1,4-butanediol, or a mixture thereof, is used. As the diacid, all known diacids can be used, such as linear or branched diacids having 4 to 12 carbon atoms, or a mixture thereof.

[0024] Furthermore, polyether polyols, such as polyether polyols based on commonly known starting materials and conventional alkylene oxides, preferably ethylene oxide, propylene oxide and / or butylene oxide, more preferably 1,2-propylene oxide and ethylene oxide, especially polyoxytetramethylene glycol, can be used for the purposes of the present invention. The advantage of polyether polyols is, inter alia, their relatively high hydrolytic stability.

[0025] Polyether alcohols with low unsaturation are also suitable. For the purposes of the present invention, polyols with low unsaturation are particularly polyether alcohols with an unsaturated compound content of less than 0.02 meq / g, preferably less than 0.01 meq / g. Such polyether alcohols are usually prepared by adding alkylene oxides, particularly ethylene oxide, propylene oxide, and mixtures thereof, to the above-mentioned diols or triols in the presence of a highly active catalyst.

[0026] Such highly active catalysts are preferably cesium hydroxide and multimetal cyanide catalysts, also known as DMC catalysts. One frequently and preferably used DMC catalyst is zinc hexacyanocobaltate. The DMC catalyst can be left in the polyether alcohol after the reaction, but is usually removed, for example, by settling or filtration.

[0027] Furthermore, polytetrahydrofuran, for example, polytetrahydrofuran having an average molecular weight Mn in the range of 400 to 1800 g / mol, preferably polytetrahydrofuran having an average molecular weight Mn in the range of 600 to 1500 g / mol, more preferably polytetrahydrofuran having an average molecular weight Mn in the range of 750 to 1250 g / mol, for example, in the range of 900 to 1100 g / mol, can be used for the purposes of the present invention.

[0028] It has been found that compositions with a particularly advantageous property profile are obtained, particularly when polyols with an average molecular weight in the range of 900 to 1100 g / mol are used: the compositions according to the invention therefore have, firstly, a low melting point and, secondly, good low-temperature properties.

[0029] However, in the context of the present invention, the polyol composition can comprise not only the polyol (P1) and the chain extenders (KV1) and (KV2), but also further isocyanate-reactive compounds. For example, the polyol composition can comprise a further polyol having an average molecular weight Mn in the range of 800 to 1200 g / mol.

[0030] Suitable polycarbonate diols are, for example, polycarbonate diols based on alkanediols.Suitable polycarbonate diols are strictly difunctional OH-functional polycarbonate diols, preferably strictly difunctional OH-functional aliphatic polycarbonate diols.Suitable polycarbonate diols are, for example, 1,4-butanediol, 1,5-pentanediol, or 1,6-hexanediol, particularly 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane-(1,5)-diol, or mixtures thereof, particularly preferably based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or mixtures thereof. In the context of the present invention, polycarbonate diols based on 1,4-butanediol and 1,6-hexanediol, polycarbonate diols based on 1,5-pentanediol and 1,6-hexanediol, polycarbonate diols based on 1,6-hexanediol, and mixtures of two or more of these polycarbonate diols are preferably used. Suitable polycarbonate diols have an average molecular weight Mn in the range of, for example, 800 to 1200 g / mol.

[0031] It has been found that when polycarbonate diol is used, a composition suitable for applications requiring good hydrolysis resistance and good aging resistance can be obtained. Thus, the composition of the present invention not only has good low-temperature properties, but also has high hydrolysis resistance and good aging resistance when polycarbonate diol is used as the polyol.

[0032] In the context of the present invention, polyetherols are preferably used as polyols (P1).

[0033] Therefore, in a further embodiment, the present invention also provides a composition as described above, wherein the polyol (P1) is a polyetherol.

[0034] In the context of the present invention, the isocyanate composition (IZ) is used for the preparation of a thermoplastic polyurethane (TPU-1). The isocyanate composition comprises at least one polyisocyanate, preferably at least one diisocyanate.

[0035] In principle, any commonly used organic isocyanate is suitable for the purposes of the present invention. As organic isocyanates, aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates are preferred, more preferably trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis(isocyanatomethyl)cyclohexane. It is possible to use cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4- and / or 2,6-diisocyanate and / or dicyclohexylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate, diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and / or 2,6-diisocyanate (TDI), dimethylbiphenyl 3,3'-diisocyanate, 1,2-diphenylethane diisocyanate and / or phenylene diisocyanate. Particularly preferably, only 4,4'-MDI is used.

[0036] Thus, in a further embodiment, the present invention provides a composition as described above, wherein the thermoplastic polyurethane is based on diphenylmethane 4,4'-diisocyanate.

[0037] Further suitable aliphatic isocyanates are, for example, hexamethylene diisocyanate (HDI) or 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI).

[0038] According to the invention, particularly preferred isocyanates are hexamethylene diisocyanate (HDI), diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), and tolylene 2,4- and / or 2,6-diisocyanate (TDI), or 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI), particularly preferred are diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), in particular diphenylmethane 4,4'-diisocyanate.

[0039] Therefore, in a further embodiment, the present invention also provides a composition as described above, wherein the polyisocyanate composition (IZ) comprises a polyisocyanate (PI) selected from the group consisting of phenylene 1,2-, 1,3- and / or 1,4-diisocyanate, triphenylmethane 4,4',4''-triisocyanate, naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and / or 2,6-diisocyanate (TDI), biphenyl 2,4'-, 4,4'- and / or 2,2-diisocyanate, diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), polyphenylpolymethylene polyisocyanate, xylylene 1,2-, 1,3- and / or 1,4-diisocyanate and m-tetramethylxylylene diisocyanate (TMXDI).

[0040] In addition to the isocyanate composition (IZ) and the polyol composition (PZ), further components, such as suitable catalysts or auxiliaries, can be used in the preparation of the thermoplastic polyurethane (TPU1).

[0041] In a preferred embodiment, catalysts that promote the reaction of the NCO groups of diisocyanates with the hydroxyl groups of isocyanate-reactive compounds and chain extenders are tertiary amines, particularly triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, and diazabicyclo[2.2.2]octane; in other preferred embodiments, they are organometallic compounds, such as titanate esters, iron compounds, preferably iron(III) acetylacetonate, tin compounds, preferably tin diacetate, tin dioctoate, and tin dilaurate, or dialkyltin salts of aliphatic carboxylic acids, preferably dibutyltin diacetate and dibutyltin dilaurate, or bismuth salts in which the bismuth is preferably in the oxidation state 2 or 3, especially 3. Salts of carboxylic acids are preferred. Carboxylic acids having 6 to 14 carbon atoms, particularly preferably 8 to 12 carbon atoms, are used as carboxylic acids. Examples of suitable bismuth salts are bismuth(III) neodecanoate, bismuth 2-ethyl-hexanoate and bismuth octanoate.

[0042] The catalyst is preferably used in an amount of 0.0001 to 0.1 parts by weight per 100 parts by weight of isocyanate-reactive compound. Preferably, a tin catalyst, in particular tin dioctoate, is used.

[0043] In addition to catalyst, it is also possible to add conventional auxiliaries.For example, surface active substances, fillers, additional flame retardants, nucleating agents, oxidation stabilizers, lubricants and demolding aids, dyes and pigments, and optionally, for example, stabilizers against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers.Suitable auxiliaries and additives can be found, for example, in Kunststoffhandbuch, Volume VII, edited by Vieweg and Hoechtlen, Carl Hanser Verlag, Munich, 1966 (pages 103-113).

[0044] Suitable methods for producing thermoplastic polyurethanes are disclosed, for example, in EP 0 922 552 A1, DE 101 03 424 A1, or WO 2006 / 072461 A1. Production is generally carried out in a belt or reactive extruder, but on a laboratory scale, it can also be carried out, for example, by manual casting. Depending on the material properties of the components, they are all directly mixed together, or the individual components are premixed and / or pre-reacted, for example, to form a prepolymer, and then subjected to polyaddition. In a further embodiment, the thermoplastic polyurethane is first produced from the preformed components using a catalyst, which can optionally incorporate a thermoplastic polyurethane auxiliary. Next, at least one filler is incorporated into this material and uniformly dispersed. This uniform dispersion is preferably carried out in an extruder, preferably a twin-screw extruder. According to the present invention, the filler is preferably added partially, for example, at the inlet of the extruder, and a further portion at a second metering position, for example, a side feeder. To set the hardness of the TPU, the amounts of forming components (b) and (c) used can be varied within a relatively wide range of molar ratios, and generally, as the chain extender content increases, the hardness increases.

[0045] According to the present invention, the mixing ratio of the components used in the production of thermoplastic polyurethanes can vary within a wide range, for example, the chain extender and polyol can be used in a molar mixing ratio of 20:1 to 1:1, preferably 18:1 to 2:1, more preferably 17:1 to 3:1, and particularly preferably 15:1 to 4:1.

[0046] According to the present invention, the mixing ratio of the chain extenders (KV1) and (KV2) used can vary within a wide range. For example, the chain extenders can be used in a molar mixing ratio of KV1:KV2 in the range of 20:1 to 3:1, preferably in the range of 15:1 to 4:1, more preferably in the range of 17:1 to 3:1, and particularly preferably in the range of 15:1 to 4:1.

[0047] The thermoplastic polyurethanes used according to the invention preferably have a hardness, determined in accordance with DIN ISO 7619-1 (Shore hardness test A(3s)), in the range of 40D to 90D, preferably in the range of 50D to 90D, determined in accordance with DIN ISO 7619-1, more preferably in the range of 60D to 90D, determined in accordance with DIN ISO 7619-1, particularly preferably in the range of 70D to 90D, determined in accordance with DIN ISO 7619-1.

[0048] Therefore, in a further embodiment, the present invention also provides the composition as described above, wherein the thermoplastic polyurethane has a Shore hardness in the range of 40D to 90D, determined according to DIN ISO 7619-1.

[0049] To prepare the thermoplastic polyurethanes of the invention, the former components are reacted, preferably in the presence of a catalyst and, optionally, auxiliaries and / or additives, in amounts such that the equivalent ratio of the NCO groups of the diisocyanate to the sum of the hydroxyl groups of the further former components is 0.9 to 1.1:1, preferably 0.95 to 1.05:1, in particular about 0.95 to 1.00:1.

[0050] The composition of the present invention comprises at least one thermoplastic polyurethane (TPU1) in an amount ranging from 40% to 60% by weight, based on the total composition, in particular from 45% to 55% by weight, based on the total composition, and preferably in each case from 48% to 52% by weight, based on the total composition.

[0051] Therefore, in a further embodiment, the present invention provides the above composition, wherein the proportion of thermoplastic polyurethane in the composition is in the range of 40% by mass to 60% by mass based on the total composition.

[0052] Here, the sum of all components of the composition in each case is 100% by weight.

[0053] According to the present invention, the average molecular weight (M) is preferably in the range of 50,000 to 500,000 Da. WThe thermoplastic polyurethane has an average molecular weight (M W The upper limit of the average molecular weight (M) is generally determined by processability and the desired property spectrum. More preferably, the thermoplastic polyurethane has an average molecular weight (M) in the range of 50,000 to 250,000 Da, and particularly preferably in the range of 50,000 to 150,000 Da. W )

[0054] According to the invention, it is also possible for the composition to comprise two or more thermoplastic polyurethanes which differ, for example, with respect to their average molecular weight or with respect to their chemical composition.

[0055] Thermoplastic polyurethanes can be produced discontinuously or continuously by known methods, for example, using a reactive extruder or belt process, by a one-shot or prepolymer process, preferably by a one-shot process. In these processes, the reacting components can be mixed together continuously or simultaneously, and the reaction begins immediately. In the extruder process, the components are introduced into an extruder, for example, individually or as a mixture, preferably at a temperature of 100°C to 280°C, and reacted, more preferably at a temperature of 140°C to 250°C, and the resulting polyurethane is then extruded, cooled, and pelletized.

[0056] The composition of the present invention further comprises a filler (F1). According to the present invention, the chemical nature and shape of the filler (F1) can vary within a wide range, as long as sufficient compatibility with the thermoplastic polyurethane (TPU-1) is ensured. Here, the filler (F1) is selected so that its shape and particle size allow sufficient miscibility and uniform dispersion in the composition.

[0057] Suitable fillers include, for example, glass fibers, glass spheres, carbon fibers, aramid fibers, potassium titanate fibers, fibers composed of liquid crystal polymers, organic fibrous fillers, and inorganic reinforcing materials. Organic fibrous fillers include, for example, cellulose fibers, hemp fibers, sisal, and kenaf. Inorganic reinforcing materials include, for example, ceramic fillers such as aluminum nitride and boron nitride, or mineral fillers such as asbestos, talc, wollastonite, microbite, silicates, chalk, calcined kaolin, mica, and quartz powder. According to the present invention, the filler (F1) is preferably selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, fibers composed of liquid crystal polymers, metal fibers, polyester fibers, polyamide fibers, organic fibrous fillers, and inorganic fibrous fillers.

[0058] Therefore, in a further embodiment, the present invention also provides the above composition, wherein the filler (F1) is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, fibers composed of liquid crystal polymers, metal fibers, polyester fibers, polyamide fibers, organic fibrous fillers and inorganic fibrous fillers.

[0059] For the purposes of the present invention, fibrous fillers are preferred. Thus, in a further embodiment, the present invention also provides a composition as described above, wherein the filler (F1) is fibrous.

[0060] The dimensions of the fillers used can vary within the usual ranges. Preferably, the fillers used have a length in the range of 3 mm to 4 mm and a diameter in the range of 1 μm to 20 μm, in each case determined according to ASTM D578-98. Thus, in a further embodiment, the present invention also provides a composition as described above, in which the filler (F1) has a length in the range of 3 mm to 4 mm and a diameter in the range of 1 μm to 20 μm, in each case determined according to ASTM D578-98.

[0061] Fillers, such as fibrous fillers, can be pretreated, for example with a silane compound, to obtain better compatibility with the thermoplastic polymer.

[0062] Preferably, an inorganic fibrous filler is used. When an inorganic fibrous filler is used, a relatively large reinforcing effect and a relatively high heat distortion resistance are observed.

[0063] According to the invention, the composition may also contain two or more fillers.

[0064] The proportion of the filler (F1) in the composition is, for example, in the range of 40% by mass to 60% by mass based on the entire composition, preferably in the range of 45% by mass to 55% by mass based on the entire composition, and more preferably in the range of 48% by mass to 52% by mass based on the entire composition.

[0065] Therefore, in a further embodiment, the present invention also provides the above composition, wherein the filler (F1) is contained in an amount ranging from 40% by mass to 60% by mass based on the total mass of the composition.

[0066] According to the invention, the composition may also comprise, in addition to the thermoplastic polyurethane (TPU1) and the filler (F1), further ingredients, such as mold release agents, UV protection agents, antioxidants or color pigments.

[0067] According to a further aspect, the present invention also provides a method for producing a composition, the method comprising: (i) the following ingredients: (a) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of a polyisocyanate composition (IZ) with a polyol composition (PZ), the polyol composition (PZ) comprising at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), and (b) Filler (F1) The method includes a step of mixing the above components.

[0068] With regard to the preferred embodiment, reference is made to what has been said above with regard to the components preferably used.

[0069] Suitable methods for preparing the compositions are known per se to the person skilled in the art. For the purposes of the present invention, methods known per se are usually used for the formulation.

[0070] For example, the composition can be produced in a manner known per se in an extruder, for example a twin-screw extruder. According to the invention, the filler is preferably added in portions, for example, at the inlet of the extruder and a further portion at a second metering point, for example a side feeder. Here, the temperature is preferably in the range of 160 to 230°C. For the purposes of the invention, the extruder can be operated at a rotation speed in the range of 150 to 300 revolutions per minute, for example.

[0071] The present invention further provides compositions obtained or obtainable by the methods of the present invention.

[0072] The present invention also provides the use of the composition of the present invention, or of a composition obtained or obtainable by a process according to the present invention, for the manufacture of a shaped body.

[0073] Preferably, the production is carried out by injection molding, calendering, powder sintering or extrusion from pellets and / or by further expansion of the composition of the invention.

[0074] According to a further aspect, the present invention further provides a shaped body comprising a composition according to the present invention or a composition obtained or obtainable by a method according to the present invention.

[0075] The present invention also provides the use of the inventive composition described above for the production of molded bodies, such as footwear parts or ski boot parts.

[0076] Further embodiments of the present invention are set forth in the claims and in the examples. It goes without saying that the above-mentioned features of the object / method according to the invention or the use method according to the invention and the features described below can be used not only in the combinations shown in each case but also in other combinations without departing from the scope of the present invention. Thus, for example, a combination of a preferred feature with a particularly preferred feature, or a combination of a feature not characterized in more detail with a particularly preferred feature, etc., is implicitly encompassed even if this combination is not explicitly mentioned.

[0077] Exemplary embodiments of the present invention are listed below, but are not intended to limit the present invention. In particular, the present invention also encompasses embodiments resulting from the back references and combinations shown below.

[0078] 1. (a) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of a polyisocyanate composition (IZ) with a polyol composition (PZ), said polyol composition (PZ) comprising at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), and (b) Filler (F1) A composition comprising:

[0079] 2. The composition according to embodiment 1, wherein the chain extender (KV1) and / or the chain extender (KV2) is selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol, diethylene glycol, triethylene glycol, hydroquinone bis-2-hydroxyethyl ether and bis(2-hydroxyethyl) terephthalate.

[0080] 3. The composition of any one of the preceding claims, wherein the chain extender (KV1) is 1,4-butanediol.

[0081] 4. The composition according to any one of the preceding claims, wherein the chain extender (KV1) is 1,4-butanediol and the chain extender (KV2) is 1,3-propanediol.

[0082] 5. The composition according to any one of the preceding claims, wherein the polyol (P1) is a polyether polyol.

[0083] 6. (a) Thermoplastic polyurethane (TPU-1) obtained or obtainable by reacting a polyisocyanate composition (IZ) with a polyol composition (PZ), said polyol composition (PZ) comprising at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), and (b) Filler (F1) A composition comprising: A composition wherein the chain extender (KV1) is 1,4-butanediol, the chain extender (KV2) is 1,3-propanediol, and the polyol (P1) is a polyether polyol.

[0084] 7. The composition of any one of the preceding claims, wherein the polyisocyanate composition (IZ) comprises a polyisocyanate (PI) selected from the group consisting of phenylene 1,2-, 1,3- and / or 1,4-diisocyanate, triphenylmethane 4,4',4''-triisocyanate, naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and / or 2,6-diisocyanate (TDI), biphenyl 2,4'-, 4,4'- and / or 2,2-diisocyanate, diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), polyphenylpolymethylene polyisocyanate, xylylene 1,2-, 1,3- and / or 1,4-diisocyanate, and m-tetramethylxylylene diisocyanate (TMXDI).

[0085] 8. The composition of any one of the preceding claims, wherein the filler (F1) is fibrous.

[0086] 9. The composition of any one of the preceding claims, wherein the filler (F1) is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, fibers composed of liquid crystal polymers, metal fibers, polyester fibers, polyamide fibers, organic fibrous fillers, and inorganic fibrous fillers.

[0087] 10. The composition according to any one of the preceding claims, wherein the filler (F1) has a length in the range of 3 mm to 4 mm and a diameter in the range of 1 μm to 20 μm, in each case determined according to ASTM D578-98.

[0088] 11. (a) Thermoplastic polyurethane (TPU-1) obtained or obtainable by reacting a polyisocyanate composition (IZ) with a polyol composition (PZ), said polyol composition (PZ) comprising at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), and (b) Filler (F1) A composition comprising: the chain extender (KV1) is 1,4-butanediol, the chain extender (KV2) is 1,3-propanediol, and the polyol (P1) is a polyether polyol; A composition in which the filler (F1) is fibrous and has a length ranging from 3 mm to 4 mm and a diameter ranging from 1 μm to 20 μm, in each case determined according to ASTM D578-98.

[0089] 12. The composition according to any one of the preceding claims, wherein the filler (F1) is contained in an amount ranging from 40% to 60% by weight based on the total weight of the composition.

[0090] 13. (a) Thermoplastic polyurethane (TPU-1) obtained or obtainable by reacting a polyisocyanate composition (IZ) with a polyol composition (PZ), said polyol composition (PZ) comprising at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), and (b) Filler (F1) A composition comprising: the chain extender (KV1) is 1,4-butanediol, the chain extender (KV2) is 1,3-propanediol, and the polyol (P1) is a polyether polyol; A composition, wherein the filler (F1) is contained in an amount in the range of 40% by mass to 60% by mass based on the entire composition.

[0091] 14. The composition of any one of the preceding claims, wherein the thermoplastic polyurethane has a Shore hardness, determined according to DIN ISO 7619-1, in the range of 40D to 90D, preferably 70D to 90D.

[0092] 15. A method for producing a composition, comprising: (i) the following ingredients: (a) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of a polyisocyanate composition (IZ) with a polyol composition (PZ), the polyol composition (PZ) comprising at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), and (b) Filler (F1) The method comprising the step of mixing

[0093] 16. The method according to embodiment 15, wherein the chain extender (KV1) and / or the chain extender (KV2) is selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol, diethylene glycol, triethylene glycol, hydroquinone bis-2-hydroxyethyl ether and bis(2-hydroxyethyl) terephthalate.

[0094] 17. The method of embodiment 15 or 16, wherein the chain extender (KV1) is 1,4-butanediol.

[0095] 18. The method of any one of embodiments 15 to 17, wherein the polyol (P1) is a polyether polyol.

[0096] 19. The method of any one of embodiments 15 to 18, wherein the polyisocyanate composition (IZ) comprises a polyisocyanate (PI) selected from the group consisting of phenylene 1,2-, 1,3- and / or 1,4-diisocyanate, triphenylmethane 4,4',4''-triisocyanate, naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and / or 2,6-diisocyanate (TDI), biphenyl 2,4'-, 4,4'- and / or 2,2-diisocyanate, diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), polyphenylpolymethylene polyisocyanate, xylylene 1,2-, 1,3- and / or 1,4-diisocyanate, and m-tetramethylxylylene diisocyanate (TMXDI).

[0097] 20. The method of any one of embodiments 15 to 19, wherein the filler (F1) is fibrous.

[0098] 21. The method of any one of embodiments 15 to 20, wherein the filler (F1) is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, fibers composed of liquid crystal polymers, metal fibers, polyester fibers, polyamide fibers, organic fibrous fillers, and inorganic fibrous fillers.

[0099] 22. The method according to any one of embodiments 15 to 21, wherein the filler (F1) has a length in the range of 3 mm to 4 mm and a diameter in the range of 1 μm to 20 μm, in each case determined according to ASTM D578-98.

[0100] 23. The method according to any one of embodiments 15 to 22, wherein the filler (F1) is contained in an amount ranging from 40% by weight to 60% by weight based on the total weight of the composition.

[0101] 24. The method of any one of embodiments 15 to 23, wherein the thermoplastic polyurethane has a Shore hardness, determined according to DIN ISO 7619-1, in the range of 40D to 90D, preferably 70D to 90D.

[0102] 25. A composition obtained or obtainable by a method according to any one of embodiments 15 to 24.

[0103] 26. Use of a composition according to any one of embodiments 1 to 14, or a composition obtained or obtainable by a method according to any one of embodiments 15 to 24, for the production of a shaped body.

[0104] 27. A shaped body comprising a composition according to any one of embodiments 1 to 14, or a composition obtained or obtainable by the method according to any one of embodiments 15 to 24.

[0105] The following examples serve to illustrate the invention but do not in any way limit its subject matter. [Example]

[0106] 1. Materials used Chopvantage HP3550 EC10-3,8: Glass fiber from PPG Industries Fiber Glass, Energieweg 3, 9608 PC Westerbroek, The Netherlands, E-glass, filament diameter 10 μm, length 3.8 mm.

[0107] TPU 1: TPU based on polytetrahydrofuran (PTHF) with a molecular weight (Mn) of 1000 Daltons, 1,4-butanediol, and MDI, with a Shore hardness of 60D.

[0108] TPU 2: TPU based on polytetrahydrofuran (PTHF) with a molecular weight (Mn) of 1000 Daltons, 1,4-butanediol, and MDI, with a Shore hardness of 83D.

[0109] TPU 3: TPU based on polytetrahydrofuran (PTHF) with a molecular weight (Mn) of 1000 Daltons, 1,4-butanediol, 1,3-propanediol, and MDI, with a Shore hardness of 83D.

[0110] TPU 4: A glass-fiber filled TPU with a Shore hardness of 70D made by compounding 48% glass fiber Chopvantage HP3550 EC10-3,8 into TPU 1.

[0111] TPU 5: A glass-fiber filled TPU with a Shore hardness of 75D made by compounding 48% glass fiber Chopvantage HP3550 EC10-3,8 into TPU 2 (could not be made, see Table 4).

[0112] TPU 6: A glass-fiber filled TPU with a Shore hardness of 75D made by compounding 48% glass fiber Chopvantage HP3550 EC10-3,8 into TPU 3.

[0113] 2. Manufacturing example 2.1 Manufacturing by manual casting process (TPU 1-3) The amounts of polyol and chain extender specified in the base recipe (Table 1) were weighed into a tin can and briefly blanketed with nitrogen. The can was closed with a lid and heated in an oven to approximately 90°C.

[0114] An additional oven for heat treating the polyurethane sheet was preheated to 80° C. The Teflon dish was placed on a hot plate and set to 125° C.

[0115] The calculated amount of liquid isocyanate was determined by volumetric measurement. For this purpose, the liquid isocyanate was weighed into a PE beaker (the volume of MDI was measured at a temperature of about 48 ° C) and poured into the PE beaker within 10 seconds. The beaker thus emptied was then tared and filled with the calculated amount of isocyanate. In the case of MDI, this was stored in an oven at about 48 ° C.

[0116] Additives that exist as solids at room temperature, such as hydrolysis inhibitors and antioxidants, were weighed directly.

[0117] The preheated polyol was placed on a jack under the stationary agitator, and the reactor vessel was then raised by the jack until the agitator blades were completely immersed in the polyol.

[0118] Before turning on the agitator motor, it was essential to ensure that the rotation speed regulator was at zero, and then the rotation speed was slowly increased to ensure good mixing without introducing air into the agitator.

[0119] Subsequently, additives such as antioxidants were added to the polyol.

[0120] The temperature of the reaction mixture was carefully set to 80° C. with a hot air blower.

[0121] If necessary, a catalyst was metered into the reaction mixture using a microliter syringe before adding the isocyanate. The isocyanate was then added at 80°C by introducing a pre-measured amount into the reaction mixture over 10 seconds. The mass was monitored by backweighing. Deviations of more than or less than 0.2 g from the loading amount were recorded. A stopwatch was started upon the addition of the isocyanate. Once the temperature reached 110°C, the reaction mixture was poured into a Teflon dish preheated to 125°C.

[0122] Ten minutes after starting the stopwatch, the polyurethane sheet was removed from the hot plate and stored in an oven at 80°C for 15 hours. The cooled polyurethane sheet was pulverized using a cutter mill. The granulated material was then dried at 110°C for 3 hours and stored in a dry state.

[0123] In principle, this process can be carried out by means of a reactive extruder or a belt process.

[0124] [Table 1]

[0125] [Table 2]

[0126] 2.2 Manufacturing of TPU 4-6 Table 3 below shows the compositions of the individual starting materials reported in parts by weight (pbw). In each case, the mixtures were produced using a twin-screw extruder model ZE40A from Berstorff, divided into 10 barrel sections and having a process length of 35 D. Continuous pelletization was used.

[0127] [Table 3]

[0128] [Table 4]

[0129] 3.Results Processing of TPU 2 was not possible: this material has a very high melting point range, making it impossible to produce glass fiber compounds.

[0130] TPU 4 was manufacturable, but had an E modulus of only 4080 MPa.

[0131] Surprisingly, TPU 6 was manufacturable. The E modulus was 18,300 MPa.

[0132] 4.Measurement method Shore hardness A: DIN ISO 7619-1, Shore hardness test A (3s) Tensile strength: DIN EN ISO 527 Elongation at break: DIN EN ISO 527 Tear propagation resistance: DIN ISO 34-1, B(b.

[0133] References Kunststoffhandbuch, Volume VII, edited by Vieweg and Hoechtlen, Carl Hanser Verlag, Munich 1966 (pp. 103-113) EP 0 922 552 A1 DE 101 03 424 A1 WO 2006 / 072461 A1

Claims

1. (a) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of a polyisocyanate composition (IZ) with a polyol composition (PZ), said polyol composition (PZ) comprising at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), the chain extender being used in a molar mixture ratio of KV1:KV2 ranging from 20:1 to 3:1; and (b) Filler (F1) A composition comprising:

2. 2. The composition according to claim 1, wherein the chain extender (KV1) and / or the chain extender (KV2) is selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol, diethylene glycol, triethylene glycol, hydroquinone bis-2-hydroxyethyl ether and bis(2-hydroxyethyl) terephthalate.

3. 3. The composition according to claim 1, wherein the chain extender (KV1) is 1,4-butanediol.

4. 4. The composition according to claim 1, wherein the polyol (P1) is a polyether polyol.

5. The composition according to any one of claims 1 to 4, wherein the polyisocyanate composition (IZ) comprises a polyisocyanate (PI) selected from the group consisting of phenylene 1,2-, 1,3- and / or 1,4-diisocyanate, triphenylmethane 4,4',4''-triisocyanate, naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and / or 2,6-diisocyanate (TDI), biphenyl 2,4'-, 4,4'- and / or 2,2-diisocyanate, diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), polyphenylpolymethylene polyisocyanate, xylylene 1,2-, 1,3- and / or 1,4-diisocyanate, and m-tetramethylxylylene diisocyanate (TMXDI).

6. 6. The composition according to claim 1, wherein the filler (F1) is fibrous.

7. 7. The composition according to claim 1, wherein the filler (F1) is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, fibers composed of liquid crystal polymers, metal fibers, polyester fibers, polyamide fibers, organic fibrous fillers, and inorganic fibrous fillers.

8. 8. Composition according to any one of claims 1 to 7, wherein the filler (F1) has a length in the range of 3 mm to 4 mm and a diameter in the range of 1 μm to 20 μm, in each case determined according to ASTM D578-98.

9. The composition according to any one of claims 1 to 8, wherein the filler (F1) is contained in an amount ranging from 40% by mass to 60% by mass based on the total amount of the composition.

10. 10. The composition according to any one of claims 1 to 9, wherein the thermoplastic polyurethane has a Shore hardness, determined according to DIN ISO 7619-1, in the range of 40D to 90D, preferably 70D to 90D.

11. 1. A method for producing a composition, comprising: (i) the following components: (a) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of a polyisocyanate composition (IZ) with a polyol composition (PZ), said polyol composition (PZ) comprising at least one polyol (P1), a chain extender (KV1) and a chain extender (KV2), the chain extender being used in a molar mixture ratio of KV1:KV2 ranging from 20:1 to 3:1; and (b) Filler (F1) The method comprising the step of mixing

12. 12. A composition obtained or obtainable by the method of claim 11.

13. 12. Use of a composition according to any one of claims 1 to 10 or a composition obtained or obtainable by the method according to claim 11 for the manufacture of a moulded body.

14. 12. A shaped body comprising a composition according to any one of claims 1 to 10, or a composition obtained or obtainable by the method according to claim 11.

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