Process for producing thermoplastic polyurethanes

Abstract

The present invention relates to a composition comprising a thermoplastic polyurethane which is the reaction product of at least one diisocyanate (II), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having secondary terminal hydroxyl groups; and the composition further comprises a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates. The present invention also relates to a process for the production of said composition and to the use of the composition according to the invention for the production of extruded, injection-molded and pressed articles and foams, shoe soles, cable sheaths, hoses, profiles, conveyor belts, fibers, nonwovens, films, moldings, plugs, housings, damping elements for the electrical industry, the automotive industry, mechanical engineering, 3-D printing, medicine and consumer goods, in particular for the production of injection-molded products, extruded products, films, profiles and shaped articles. The present invention also relates to a shaped article comprising the composition according to the invention.

Description

[0001] This invention relates to a composition comprising a thermoplastic polyurethane, which is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having secondary terminal hydroxyl groups; and the composition further comprises a component (CC) selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably selected from the group consisting of bismuth carboxylate. The invention also relates to a method for preparing the composition and the use of the composition according to the invention in the production of extruded, injection-molded, and pressed articles, as well as foams, shoe soles, cable sheaths, hoses, profiles, drive belts, fibers, nonwovens, films, molded articles, plugs, housings, damping elements for the electrical industry, automotive industry, mechanical engineering, 3D printing, pharmaceuticals, and consumer products, particularly for the production of injection-molded products, extruded products, films, profiles, and molded articles. The invention further relates to a molded article comprising the composition according to the invention.

[0002] Thermoplastic polyurethane elastomers (TPUs) are of great industrial importance due to their excellent mechanical properties and adaptability to cost-effective thermoplastic processing. Variations in input materials allow for the acquisition of different property profiles. The synthesis of thermoplastic processable polyurethane elastomers can be achieved in a stepwise manner (prepolymer stoichiometry) or by reacting all components simultaneously in one stage (one-step stoichiometry). Thermoplastic polyurethanes for a wide range of applications are known in principle from the prior art.

[0003] Polypropylene glycol (PPG) is an interesting input material for the production of thermoplastic polyurethanes due to its low cost. In conventional continuous processes, the use of unmodified PPG is disadvantageous because the low reactivity of the secondary OH groups leads to slow molecular weight growth.

[0004] The use of polypropylene glycol as an input material in the production of thermoplastic polyurethanes is disclosed, for example, in WO 02 / 064656A2. Thermoplastic polyurethanes are produced in a one-step process using polyols with a high proportion of secondary hydroxyl groups. WO 93 / 24549 A1 and US 2006 / 0258831 A1 also disclose one-step processes for producing thermoplastic polyurethanes using polyols with secondary OH groups.

[0005] EP 1746117 A1 discloses a method for producing isocyanate-containing prepolymers with low monomeric isocyanate content by reacting a diisocyanate with at least one compound having more than two isocyanate reactive hydrogen atoms and optionally subsequently removing unconverted monomeric diisocyanate. A one-step method using the prepolymer is disclosed.

[0006] In methods known from the prior art, it is generally difficult to adjust the block length, and therefore difficult to adjust the properties of the resulting polymer. Therefore, an object of the present invention is to provide a thermoplastic polyurethane and a method for producing the same, which can use polypropylene glycol and exhibits good mechanical properties. Another object of the present invention is to provide a cost-effective method for producing the corresponding polymer.

[0007] According to the present invention, this objective is achieved by a composition comprising...

[0008] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0009] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0010] Specifically, this objective is achieved by a composition comprising...

[0011] (i) A thermoplastic polyurethane, said thermoplastic polyurethane being a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), said polyol composition comprising a polyol (PA) having a secondary hydroxyl group, said polyol (PA) being selected from the group consisting of polypropylene glycol, and

[0012] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0013] In another aspect, the present invention also provides a method for preparing a composition comprising...

[0014] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, preferably wherein the polyol (PA) is selected from the group consisting of polypropylene glycol, and

[0015] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0016] The compositions according to the invention comprise thermoplastic polyurethane and component (CC), but may also comprise other components. According to the invention, the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group.

[0017] Surprisingly, compositions according to the invention comprising component (CC) and thermoplastic polyurethane exhibit excellent mechanical properties, which can be produced using cost-effective polypropylene glycol with a high proportion of secondary terminal OH groups, and yields a transparent product. Advantageous properties such as, for example, low abrasion, high tensile strength, high resistance to tear propagation, and high softening temperature (TMA initiation) can be obtained.

[0018] In the context of this invention, unless otherwise stated, the mechanical properties were previously measured on injection-molded plates that had been heat-treated at 100°C for 20 hours.

[0019] The composition comprises a thermoplastic polyurethane, which is the product of a reaction of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having secondary hydroxyl groups. Thermoplastic polyurethanes and methods for their preparation are known in principle. According to the present invention, the polyol composition (PC) comprises a polyol (PA) having secondary hydroxyl groups.

[0020] Polyols having secondary hydroxyl groups are also known in principle. Suitable polyols (PAs) containing secondary hydroxyl groups can, for example, contain more than 85% secondary hydroxyl groups, such as more than 90% secondary hydroxyl groups, particularly more than 94% secondary hydroxyl groups, more preferably more than 95% secondary hydroxyl groups, or even up to 100% secondary hydroxyl groups. According to another embodiment, the invention also relates to compositions disclosed above, wherein the polyol (PA) contains more than 94% secondary hydroxyl groups, preferably more than 98%, particularly more than 99%.

[0021] Propylene glycol is particularly suitable. According to another embodiment, the invention also relates to compositions disclosed above, wherein the polyol (PA) is selected from the group consisting of polypropylene glycols.

[0022] Suitable polypropylene glycols according to the invention include those having a number average molecular weight Mn in the range of 650 g / mol to 3500 g / mol, particularly in the range of 1000 g / mol to 3000 g / mol, and more preferably in the range of 1000 g / mol to 1600 g / mol.

[0023] It has been found that polypropylene glycol with particularly high molecular weights (e.g., average molecular weight Mn greater than 3000 or greater than 2000) results in less favorable mechanical properties of the resulting thermoplastic polyurethane.

[0024] The polyol used preferably has a polydispersity Pd of less than 1.4, more preferably less than 1.2.

[0025] According to another embodiment, the present invention also relates to the compositions disclosed above, wherein the number-average molecular weight of the polyol (PA) is in the range of 1000 g / mol to 3000 g / mol.

[0026] In another embodiment, the present invention therefore also provides a thermoplastic polyurethane as described above, wherein the polypropylene glycol has a number-average molecular weight Mn in the range of 1000 g / mol to 1600 g / mol and a polydispersity Pd of less than 1.5.

[0027] The functionality of propylene glycol is preferably in the range of 1.95 to 2.0, and more preferably in the range of 1.98 to 2.0.

[0028] Suitable propylene glycol can be prepared, for example, using a DMC catalyst. Suitable methods are known to those skilled in the art.

[0029] The polyol composition (PC) may contain additional components, such as, for example, additional polyols, particularly additional polyols having primary hydroxyl groups. According to another embodiment, the invention also relates to compositions disclosed above, wherein the polyol composition further comprises a polyol (PB) having primary hydroxyl groups, particularly a polyol (PB) having at least 80% primary hydroxyl groups.

[0030] The proportion of polyols in a polyol composition can vary over a wide range. Preferably, based on a polyol composition (PC) of 100 mol%, the polyol composition contains more than 50 mol% of polyol (PA). According to another embodiment, the invention also relates to compositions disclosed above, wherein based on a polyol composition (PC) of 100 mol%, the content of polyol (PA) in the polyol composition is more than 50 mol%, preferably more than 70 mol%, for example, in the range of 50 mol% to 100 mol% based on a polyol composition (PC) of 100 mol%, preferably in the range of 70 mol% to 95 mol% based on a polyol composition (PC) of 100 mol%.

[0031] Other suitable polyols (PB) are known in principle to those skilled in the art and described, for example, in "Kunststoffhandbuch, Vol. 7, Polyurethane", Carl Hanser Verlag, 3rd edition, 1993, Chapter 3.1. Polyester alcohols or polyether alcohols are particularly preferred as additional polyols. According to the invention, not only PTHF, but other other polyethers or polyesters are also suitable. Polyether polyols are particularly preferred. The number-average molecular weight of the polyols used according to the invention is preferably between 250 g / mol and 2000 g / mol.

[0032] According to another embodiment, the present invention also relates to the compositions disclosed above, wherein the polyol (PB) is selected from the group consisting of polyether polyols.

[0033] According to the present invention, the preferred polyether alcohols are polyethylene glycol and polytetrahydrofuran. According to the present invention, mixtures of various polyether alcohols, such as two or more polytetrahydrofurans with different molecular weights, can also be used.

[0034] Suitable examples include polytetrahydrofuran (PTHF) with a molecular weight Mn in the range of 750 g / mol to 2500 g / mol, more preferably in the range of 800 g / mol to 2000 g / mol, and even more preferably in the range of 850 g / mol to 1600 g / mol.

[0035] According to another embodiment, the present invention also relates to compositions as disclosed above, wherein the number average molecular weight of the polyol (PB) is 0.75 × 10⁻⁶. 3 g / mol up to 2.5 × 10 3 Within the range of g / mol.

[0036] It has been found that thermoplastic polyurethanes have improved properties when the molecular weight or polarity of polyols (PA) and polyols (PB) are in similar ranges.

[0037] Preferably, the molecular weights of the polyols (PA) and (PB) are adjusted. Preferably, the molecular weight of the polyol (PB) is within the same range as or lower than the molecular weight of the polyol (PA). Typically, the molecular weight of the polyol (PB) is in the range of 1000 g / mol higher than or lower than the molecular weight of the polyol (PA).

[0038] The ratio of polyol (PA) to polyol (PB) in a polyol composition can vary over a wide range, for example, from 9:1 to 1:9. According to another embodiment, the invention also relates to compositions disclosed above, wherein the ratio of polyol (PA) to (PB) is in the range of 9:1 to 1:9.

[0039] To prepare thermoplastic polyurethanes, chain extenders are used. Suitable chain extenders are, for example, those with a molecular weight <500 g / mol. In the context of this invention, this is the weight-average molecular weight. Chain extenders used in the context of this invention can be, for example, compounds having hydroxyl or amino groups, especially compounds having two hydroxyl or amino groups. However, according to the invention, mixtures of different compounds can also be used as chain extenders. According to the invention, the average functionality of the mixture is 2.

[0040] According to the present invention, compounds having hydroxyl groups are preferably used as chain extenders, especially diols. Aliphatic, arylita-aliphatic, aromatic, and / or alicyclic diols with a molecular weight of 50 g / mol to 220 g / mol are preferred. Alkyl diols having 2 to 10 carbon atoms in the alkylene group are preferred, especially diallyl glycols, trialkyl glycols, tetraalkyl glycols, pentaalkyl glycols, hexanediols, heptaalkyl glycols, octaalkyl glycols, nonaalkyl glycols, and / or decaalkyl glycols. Particularly preferred for the present invention are 1,2-ethylene glycol, propane-1,3-diol, butane-1,4-diol, and hexane-1,6-diol. Aromatic compounds, such as hydroxyquinone bis(2-hydroxyethyl) ether, may also be used.

[0041] According to the invention, compounds having amino groups, such as diamines, can also be used. Similarly, mixtures of diols and diamines can also be used.

[0042] The chain extender is preferably a diol with a molecular weight Mw < 220 g / mol. According to the present invention, transparent thermoplastic polyurethane can be prepared using only one diol with a molecular weight Mw < 220 g / mol.

[0043] In another embodiment, more than one diol is used as a chain extender. Therefore, a mixture of chain extenders can also be used.

[0044] The chain extender is preferably used in an amount such that the molar ratio of the sum of the functionalities of the polyol composition (PC) and the chain extender to the sum of the functionalities of the diisocyanate (I1) is in the range of 1:0.8 to 1:1.3, more preferably in the range of 1:0.9 to 1:1.2, for example in the range of 1:0.95 to 1:1.15.

[0045] To prepare thermoplastic polyurethane, diisocyanate (I1) is used.

[0046] Suitable diisocyanates are known to those skilled in the art. According to the invention, at least one diisocyanate is used. According to the invention, a mixture of two or more diisocyanates may also be used.

[0047] In the context of this invention, preferred diisocyanates are aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates.

[0048] The aliphatic diisocyanates used are conventional aliphatic and / or alicyclic diisocyanates, such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, trimethylhexamethylene 1,6-diisocyanate, and 1-isocyanate. 3,3,5-trimethyl-5-isocyanate-methylcyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanate-methyl)cyclohexane and / or 1,3-bis(isocyanate-methyl)cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4-diisocyanate and / or 1-methylcyclohexane 2,6-diisocyanate, methylene dicyclohexyl 4,4'-diisocyanate, methylene dicyclohexyl 2,4'-diisocyanate and / or methylene dicyclohexyl 2,2'-diisocyanate (H12MDI).

[0049] Preferred aliphatic diisocyanates are hexamethylene 1,6-diisocyanate (HDI), 1-isocyano-3,3,5-trimethyl-5-isocyano-methylcyclohexane and methylene dicyclohexyl 4,4'-diisocyanate, methylene dicyclohexyl 2,4'-diisocyanate and / or methylene dicyclohexyl 2,2'-diisocyanate (H12MDI); particularly preferred are methylene dicyclohexyl 4,4'-diisocyanate, methylene dicyclohexyl 2,4'-diisocyanate and / or methylene dicyclohexyl 2,2'-diisocyanate (H12MDI) and 1-isocyano-3,3,5-trimethyl-5-isocyano-methylcyclohexane or mixtures thereof.

[0050] Suitable aromatic diisocyanates, especially diphenylmethane 2,2'-diisocyanate, diphenylmethane 2,4'-diisocyanate and / or diphenylmethane 4,4'-diisocyanate (MDI), naphthylene 1,5-diisocyanate (NDI), toluene 2,4-diisocyanate and / or toluene 2,6-diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanate cyclophenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethane 4,4'-diisocyanate (EDI), diphenylmethane diisocyanate, dimethyl diphenyl 3,3'-diisocyanate, diphenylethane 1,2-diisocyanate and / or phenylene diisocyanate. Preferred aromatic diisocyanates are diphenylmethane 2,2'-diisocyanate, diphenylmethane 2,4'-diisocyanate and / or diphenylmethane 4,4'-diisocyanate (MDI) and mixtures thereof.

[0051] In a preferred embodiment, the diisocyanate (I1) is selected from the group consisting of: methylene diphenyl diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI), 1,5-naphthylene diisocyanate (NDI), 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanate biphenyl (TODI), p-phenylene diisocyanate (PDI), 1-isocyanate 3,3,5-trimethyl-5-isocyanate methylcyclohexane (isophorone diisocyanate, IPDI), and 4,4'-methylene dicyclohexyl diisocyanate, 2,4'-methylene dicyclohexyl diisocyanate, and 2,2'-methylene dicyclohexyl diisocyanate (H12MDI).

[0052] Mixtures of two or more diisocyanates or mixtures of diisocyanate (I1) and other polyfunctional isocyanates can also be used. Preferred examples of polyfunctional isocyanates are triisocyanates, such as triphenylmethane 4,4',4''-triisocyanate, and cyanurates of the above diisocyanates, as well as oligomers that can be obtained by partial reaction of diisocyanates with water, such as biuret of the above diisocyanates, and oligomers that can be obtained by specific reaction of a half-terminated diisocyanate with a polyol having an average of more than two, and preferably three or more, hydroxyl groups.

[0053] According to the present invention, diisocyanate (I1) can be used in pure form or in the form of a composition comprising diisocyanate and at least one solvent. Suitable compatible non-reactive solvents are known to those skilled in the art.

[0054] In another embodiment, the present invention therefore also provides a thermoplastic polyurethane as described above, wherein the diisocyanate (I1) is selected from the group consisting of: methylene diphenyl diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI), 1,5-naphthylene diisocyanate (NDI), 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanate diphenyl (TODI), p-phenylene diisocyanate (PDI), 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane (isophorone diisocyanate, IPDI), and 4,4'-methylene dicyclohexyl diisocyanate, 2,4'-methylene dicyclohexyl diisocyanate, and 2,2'-methylene dicyclohexyl diisocyanate (H12MDI).

[0055] The properties of thermoplastic polyurethanes can vary depending on the ratio of the building components used and the preparation method. The molecular weight of thermoplastic polyurethanes can be determined by gel permeation chromatography (GPC). Preferably, the thermoplastic polyurethane has a molecular weight greater than 1.2 × 10⁻⁶, as determined by gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021. 5 The weight-average molecular weight (g / mol) excluding urethane crosslinking.

[0056] Measurements for determining the molecular weight of urethanes, including urethane esters, are performed using a GPC according to DIN EN ISO 13885-2:2021, with TPU dissolved in DMF (0.5% concentration). Molecular weight is typically determined using two GPC columns connected in series. Calibration is usually performed using polymethyl methacrylate, and DMF is typically used as the flow medium. Unlike DIN EN ISO 13885-2:2021, the solvent is typically not mixed with lithium bromide, and due to system stability, the column is not run at room temperature but at elevated temperatures, such as 60°C.

[0057] To determine the molecular weight excluding urethane, the TPU / DMF solution was treated with a secondary amine at elevated temperatures to cleave the urethane.

[0058] According to another embodiment, the invention also relates to compositions as disclosed above, wherein the thermoplastic polyurethane has a content of more than 1.2 × 10⁻⁶ CFU / g as determined by gel permeation chromatography (GPC) according to EN ISO 13885-2:2021. 5 The weight-average molecular weight (g / mol) excluding urethane crosslinking.

[0059] Furthermore, in the components after tempering for 20 hours at 100°C, the thermoplastic polyurethane preferably has a molecular weight Mw of more than 150 kD, more preferably more than 180 kD, and particularly preferably more than 200 kD, including urethane esters.

[0060] The ratio of the molecular weight measured with urethane to the molecular weight measured without urethane can be, for example, in the range of 2:1 to 1:1 (measured on the final component after tempering for 20 hours at 100°C).

[0061] The compositions according to the invention further comprise a component (CC) selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably selected from the group consisting of bismuth carboxylate.

[0062] Suitable options include, for example, carboxylates, wherein the carboxyl groups have 6 to 12 carbon atoms independently of each other. In the context of this invention, two or more bismuth carboxylates or zinc carboxylates may be used.

[0063] Suitable bismuth compounds include, in particular, bismuth (2-ethylhexanoate), bismuth octanoate, and / or bismuth neodecanoate. Bismuth tris(2-ethylhexanoate) and / or bismuth neodecanoate are preferred according to the invention, and more preferably bismuth neodecanoate.

[0064] Suitable zinc compounds include zinc 2-ethylhexanoate, zinc octanoate, and / or zinc neodecanoate. Zinc 2-ethylhexanoate and / or zinc neodecanoate are preferred according to the invention.

[0065] According to the present invention, mixtures of bismuth carboxylate or zinc carboxylate with other organometallic catalysts (such as titanates, iron compounds) can also be used. The compositions according to the present invention may also, for example, contain titanium organocomplexes.

[0066] Suitable are mixtures of organic complexes of bismuth carboxylate or titanium, such as bismuth neodecanoate and titanium 2-ethylhexanoate (IV), or bismuth neodecanoate and diisobutoxy-bis(ethyl)acetoacetate-titanium ester.

[0067] According to the present invention, additives or auxiliaries may also be used. The composition may also contain additional catalysts. Suitable catalysts are known from the prior art.

[0068] The compositions according to the invention may also contain additional components, such as, for example, conventional auxiliaries. Examples include surfactants, fillers, additional flame retardants, nucleating agents, oxidative stabilizers, lubricants and release agents, dyes and pigments, optional stabilizers to resist, for example, hydrolysis, light, heat or discoloration; organic and / or inorganic fillers, reinforcing agents and plasticizers. Suitable auxiliaries and adjuvants can be found, for example, in Kunststoffhandbuch, Volume VII, edited by Vieweg and Höchtlen, Carl Hanser Verlag, Munich 1966 (pp. 103-113).

[0069] The compositions according to the invention may also contain additional polymeric components, such as, for example, polystyrene, high-impact polystyrene, polyethylene, polypropylene, and polyethylene terephthalate and thermoplastic elastomers or mixtures thereof. Suitable polymeric components are known in principle. The polymeric components may be added in suitable amounts.

[0070] According to another embodiment, the present invention also relates to compositions disclosed above, wherein the compositions further comprise a thermoplastic resin selected from the group consisting of polystyrene, high-impact polystyrene, polyethylene, polypropylene, polyethylene terephthalate, and thermoplastic elastomers or mixtures thereof.

[0071] In the context of this invention, auxiliaries and / or additives may be added. They may be dissolved in one of the reaction components, preferably in the polyol component, or added to a subsequent mixing device (e.g., an extruder) once the reaction is complete.

[0072] In order to produce thermoplastic polyurethane, the synthetic components may optionally react in the presence of catalysts, auxiliaries and / or additives, preferably in an amount such that the equivalence ratio of the NCO groups to the sum of the NCO reactive groups (especially OH groups) of the low molecular weight compound and the polyol is 0.9:1.0 to 1.1:1.0, preferably 0.95:1.0 to 1.05:1.0, more preferably 0.97:1.0 to 1.05:1.0.

[0073] According to the invention, the properties of the resulting thermoplastic polyurethane can be influenced by the selection of the diisocyanate, polyol, and chain extender used. The thermoplastic polyurethane according to the invention advantageously has a Shore hardness in the range of 35A to 80D, more preferably in the range of 60A to 98A, as determined according to DIN 53505.

[0074] In another embodiment, the present invention therefore also provides a thermoplastic polyurethane as described above, wherein the thermoplastic polyurethane has a Shore hardness in the range of 50A to 80D as determined according to DIN 53505.

[0075] The thermoplastic polyurethane according to the invention is preferably opaque to transparent. In another embodiment, the invention therefore also provides a thermoplastic polyurethane as described above, wherein the thermoplastic polyurethane is opaque to transparent. The thermoplastic polyurethane having a matte surface can also be prepared according to the invention.

[0076] Typically, the compositions according to the invention are prepared in a form suitable for storage and further processing, such as in powder or molded form, particularly in pellet form. Therefore, according to another embodiment, the invention also relates to the compositions disclosed above, wherein the compositions are in pellet form.

[0077] Surprisingly, the compositions according to the invention have been found to possess advantageous properties compared to previously known polypropylene glycol-based thermoplastic polyurethanes. It has been discovered that the compositions according to the invention exhibit good cold flexibility, low abrasion, and, compared to previously known polypropylene glycol-based thermoplastic polyurethanes, higher tensile strength, higher resistance to tear propagation, lower compression set, and higher solution viscosity. Compared to previously known polyether-based thermoplastic polyurethanes, the thermoplastic polyurethanes according to the invention also possess a high softening temperature (TMA initiation).

[0078] Furthermore, the composition according to the invention exhibits good production yield in extrusion.

[0079] According to another aspect, the present invention also relates to a method for preparing the compositions disclosed above. According to the present invention, the compositions can be prepared by mixing components, namely thermoplastic polyurethane and components (CC) selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably selected from the group consisting of bismuth carboxylate, in a suitable apparatus.

[0080] According to another embodiment, the composition according to the invention can be obtained by a method for preparing thermoplastic polyurethane, preferably in the presence of a component (CC) selected from the group consisting of bismuth carboxylate and zinc carboxylate, and more preferably from the group consisting of bismuth carboxylate.

[0081] Therefore, the present invention also relates to a method for preparing a composition comprising...

[0082] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0083] (ii) Component (CC), wherein the component (CC) is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0084] According to one embodiment, the present invention relates to a method for preparing the compositions disclosed above, the method comprising mixing

[0085] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0086] (ii) Component (CC), wherein the component (CC) is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0087] According to another aspect, the present invention relates to a method for preparing a composition comprising...

[0088] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0089] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0090] The method includes the step of reacting at least one diisocyanate (I1), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group and a component (CC) selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably selected from the group consisting of bismuth carboxylate.

[0091] Suitable preparation methods are known in principle and may include mixing steps or additional processing steps. The method of the present invention may particularly include storage steps and / or heating steps.

[0092] Operating this method as a continuous process, such as an online one-step process, may be advantageous. In another embodiment, the invention therefore also provides a method as described above, wherein the method is operated as a continuous process. According to another embodiment, the invention also relates to a method as disclosed above, wherein the building components of the thermoplastic polyurethane are mixed in a continuous process.

[0093] According to the present invention, this method enables the conversion of the second terminal OH group of polypropylene glycol. For example, the temperature, reaction time, and mixing mass are optimized for this purpose. For example, the reaction can be carried out stepwise. The reaction is preferably carried out at a temperature in the range of 160°C to 250°C, and more preferably in the range of 180°C to 220°C.

[0094] The reaction according to the invention can itself be carried out in any suitable apparatus known to those skilled in the art.

[0095] For example, in a process mode in a reactive extruder, at a reaction temperature, for example, in the range of 100°C to 300°C, preferably in the range of 150°C to 250°C, and especially in the range of 160°C to 230°C, the reaction duration can be less than 20 minutes, preferably less than 10 minutes, and especially less than 5 minutes.

[0096] For example, in a belt process, at a reaction temperature, for example, in the range of 100°C to 300°C, preferably in the range of 110°C to 220°C, and especially in the range of 120°C to 200°C, the reaction duration can be less than 30 minutes, preferably less than 20 minutes, and especially less than 10 minutes.

[0097] Typically, the temperature during the mixing of the prepolymer into the reaction mixture is in the range of 60°C to 300°C, preferably in the range of 70°C to 200°C, and particularly preferably in the range of 80°C to 150°C.

[0098] According to the invention, the reaction can be carried out in a suitable apparatus, wherein suitable methods are known to those skilled in the art. Mixing of the components is carried out, for example, using a mixing apparatus, particularly a mixing apparatus operating at high shear energy. Examples include mixing heads, static mixers, nozzles, or multi-screw extruders. According to another embodiment, the invention also relates to a method as disclosed above, wherein the building components of thermoplastic polyurethane are mixed in a single apparatus. For example, static mixers, reactive extruders, or stirred tanks are suitable for the reaction according to the invention.

[0099] According to another embodiment, the invention also relates to the method disclosed above, wherein the components are mixed in an extruder. Suitable reactors or continuous production system processes can also be used.

[0100] The temperature of the extruder housing is advantageously selected so that the reactants are fully converted and any possible incorporation of additional additives / components can be carried out under the mildest possible conditions for the product.

[0101] The compositions according to the invention are suitable for a wide range of applications. Their excellent mechanical properties and good thermal behavior make the thermoplastic polyurethanes according to the invention particularly suitable for the production of extruded, injection-molded, and pressed articles, as well as foams, shoe soles, cable sheaths, hoses, profiles, drive belts, fibers, nonwovens, films, molded articles, plugs, housings, and damping elements for the electrical industry, automotive industry, mechanical engineering, 3D printing, pharmaceuticals, and consumer products, especially for the production of injection-molded products, extruded products, films, profiles, and molded articles.

[0102] On the other hand, the present invention also provides the use of thermoplastic polyurethane according to the invention, or thermoplastic polyurethane that can be obtained or acquired by the method according to the invention, for the production of extruded, injection-molded and pressed articles, as well as foams, shoe soles, cable sheaths, hoses, profiles, drive belts, fibers, nonwovens, films, molded articles, plugs, housings, for damping elements in the electrical industry, automotive industry, mechanical engineering, 3D printing, pharmaceuticals and consumer products, particularly for the production of injection-molded products, extruded products, films, profiles and molded articles.

[0103] Therefore, in another embodiment, the present invention also provides the use of the thermoplastic polyurethane according to the invention, or the thermoplastic polyurethane that can be obtained or acquired by the method according to the invention, for the production of injection-molded products, extruded products, films, profiles and molded articles as described above.

[0104] The thermoplastic polyurethane of the present invention is particularly suitable for the production of molded articles, such as extruded, injection molded and pressed articles, as well as foams, shoe soles, cable sheaths, hoses, profiles, drive belts, fibers, nonwovens, films, molded articles, plugs, housings, and damping elements for the electrical industry, automotive industry, mechanical engineering, 3D printing, pharmaceuticals and consumer products, especially for the production of injection molded products, extruded products, films, profiles and molded articles.

[0105] In another aspect, the present invention also provides a molded article comprising the composition disclosed above or a composition that can be obtained or acquired by the method according to the present invention.

[0106] Further embodiments of the invention can be found in the claims and embodiments. It should be understood that the features described above and set forth below according to the subject matter / method / use of the invention are applicable not only to the combinations specified in each case, but also to other combinations without departing from the scope of the invention. Therefore, for example, combinations of preferred features with particularly preferred features, or combinations of features not further characterized with particularly preferred features, are also implicitly covered, even if such combinations are not explicitly mentioned.

[0107] Exemplary embodiments of the invention are described below, but are by no means intended to limit the invention. The invention also includes, in particular, embodiments derived from combinations referenced in the dependent sense and therefore specified below.

[0108] The invention is further illustrated by the following groups and combinations of embodiments resulting from the indicated dependencies and reverse references. In particular, it should be noted that in each instance of reference to the scope of the embodiments, for example in the context of terms such as “the composition according to any one of embodiments 1 to 4,” each embodiment within that scope is meant to be explicitly disclosed by a person skilled in the art, i.e., the wording of the term should be understood by a person skilled in the art to be synonymous with “the composition according to any one of embodiments 1, 2, 3, and 4*.” Furthermore, it should be clearly noted that the following group of embodiments represents a suitably structured portion of the general description of preferred aspects of the invention and thus appropriately supports, but does not imply, the claims of the invention.

[0109] 1. A composition comprising:

[0110] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0111] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0112] 2. A composition comprising:

[0113] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0114] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate.

[0115] 3. A composition comprising:

[0116] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0117] (ii) Component (CC), which is selected from the group of zinc carboxylate.

[0118] 4. The composition according to any one of embodiments 1 to 3, wherein the polyol composition further comprises a polyol (PB) having at least 80% primary terminal hydroxyl groups.

[0119] 5. The composition according to any one of embodiments 1 to 4, wherein the polyol composition (PC) is 100 mol% and the polyol composition contains more than 50 mol% polyol (PA).

[0120] 6. The composition according to any one of embodiments 1 to 5, wherein the polyol (PA) contains more than 94% secondary hydroxyl groups.

[0121] 7. The composition according to any one of embodiments 1 to 6, wherein the polyol (PA) is selected from the group consisting of polypropylene glycols.

[0122] 8. The composition according to any one of embodiments 4 to 7, wherein the polyol (PB) is selected from the group consisting of polyether polyols.

[0123] 9. The composition according to any one of embodiments 1 to 8, wherein the number average molecular weight of the polyol (PA) is 1 × 10⁻⁶. 3 g / mol to 3×10 3 Within the range of g / mol.

[0124] 10. The composition according to any one of embodiments 1 to 7, wherein the number average molecular weight of the polyol (PB) is 0.75 × 10⁻⁶. 3 g / mol up to 2.5 × 10 3 Within the range of g / mol.

[0125] 11. The composition according to any one of embodiments 1 to 10, wherein the ratio of polyol (PA) and (PB) is in the range of 9:1 to 1:9.

[0126] 12. The composition according to any one of embodiments 1 to 11, wherein the thermoplastic polyurethane has a content of more than 1.2 × 10⁻⁶ as determined by gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021. 5 The weight-average molecular weight (g / mol) excluding urethane crosslinking.

[0127] 13. The composition according to any one of embodiments 1 to 12, wherein the composition further comprises a thermoplastic resin selected from the group consisting of polystyrene, high-impact polystyrene, polyethylene, polypropylene and polyethylene terephthalate, and thermoplastic elastomers or mixtures thereof.

[0128] 14. The composition according to any one of embodiments 1 to 13, wherein the composition is in pellet form.

[0129] 15. A method for preparing a composition according to any one of embodiments 1 to 14.

[0130] 16. A method for preparing a composition, said composition comprising

[0131] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0132] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0133] 17. A method for preparing a composition comprising...

[0134] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0135] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0136] The method includes the step of reacting at least one diisocyanate (I1), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group and a component (CC) selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably selected from the group consisting of bismuth carboxylate.

[0137] 18. A method for preparing a composition comprising...

[0138] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0139] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0140] The method includes the step of mixing the following components: a thermoplastic polyurethane, which is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having secondary hydroxyl groups, and

[0141] Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0142] 19. The method according to any one of embodiments 15 to 18, wherein the building components of the thermoplastic polyurethane are mixed in a continuous process.

[0143] 20. The method according to any one of embodiments 15 or 19, wherein the building components of the thermoplastic polyurethane are mixed in a device.

[0144] 21. The method according to any one of embodiments 15 to 20, wherein the components are mixed in a reactive extruder.

[0145] 22. The method according to any one of embodiments 15 to 21, wherein the polyol composition further comprises a polyol (PB) having at least 80% primary terminal hydroxyl groups.

[0146] 23. The method according to any one of embodiments 15 to 22, wherein the polyol composition (PC) is 100 mol% and the content of polyol (PA) in the polyol composition is higher than 50 mol%.

[0147] 24. The method according to any one of embodiments 15 to 23, wherein the polyol (PA) contains more than 94% secondary hydroxyl groups.

[0148] 25. The method according to any one of embodiments 15 to 24, wherein the polyol (PA) is selected from the group consisting of polypropylene glycol.

[0149] 26. The method according to any one of embodiments 15 to 25, wherein the polyol (PB) is selected from the group consisting of polyether polyols.

[0150] 27. The method according to any one of embodiments 15 to 26, wherein the number-average molecular weight of the polyol (PA) is 1 × 10⁻⁶. 3 g / mol to 3×10 3 Within the range of g / mol.

[0151] 28. The method according to any one of embodiments 15 to 27, wherein the number average molecular weight of the polyol (PB) is 0.75 × 10⁻⁶. 3 g / mol up to 2.5 × 10 3Within the range of g / mol.

[0152] 29. The method according to any one of embodiments 15 to 28, wherein the ratio of polyol (PA) and (PB) is in the range of 9:1 to 1:9.

[0153] 30. The method according to any one of embodiments 15 to 29, wherein the thermoplastic polyurethane has a content of more than 1.2 × 10⁻⁶ as determined by gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021. 5 The weight-average molecular weight (g / mol) excluding urethane crosslinking.

[0154] 31. The method according to any one of embodiments 15 to 30, wherein the composition further comprises a thermoplastic resin selected from the group consisting of polystyrene, high-impact polystyrene, polyethylene, polypropylene and polyethylene terephthalate, and thermoplastic elastomers or mixtures thereof.

[0155] 32. The method according to any one of embodiments 15 to 31, wherein the composition is in pellet form.

[0156] 33. The composition according to any one of embodiments 1 to 14 or the composition prepared by any one of embodiments 15 to 32 is used for the production of extruded, injection molded and pressed articles, as well as foams, shoe soles, cable sheaths, hoses, profiles, drive belts, fibers, nonwovens, films, molded articles, plugs, housings, for damping elements in the electrical industry, automotive industry, mechanical engineering, 3D printing, pharmaceuticals and consumer products, and particularly for the production of injection molded products, extruded products, films, profiles and molded articles.

[0157] 34. A molded article comprising a composition according to any one of embodiments 1 to 14 or a composition obtainable or acquireable by any one of embodiments 14 to 32.

[0158] 35. A composition comprising:

[0159] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having secondary hydroxyl groups, wherein the polyol (PA) contains more than 94% secondary hydroxyl groups, and

[0160] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0161] 36. The composition according to embodiment 35, wherein the polyol composition further comprises a polyol (PB) having at least 80% primary terminal hydroxyl groups.

[0162] 37. The composition according to embodiment 35 or 36, wherein the polyol composition (PC) is 100 mol% and the polyol composition contains more than 50 mol% polyol (PA).

[0163] 38. The composition according to any one of embodiments 35 to 37, wherein the polyol (PA) is selected from the group consisting of polypropylene glycols.

[0164] 39. The composition according to any one of embodiments 36 to 38, wherein the polyol (PB) is selected from the group consisting of polyether polyols.

[0165] 40. The composition according to any one of embodiments 35 to 39, wherein the number average molecular weight of the polyol (PA) is 1 × 10⁻⁶. 3 g / mol to 3×10 3 Within the range of g / mol.

[0166] 41. The composition according to any one of embodiments 35 to 40, wherein the number average molecular weight of the polyol (PB) is 0.75 × 10⁻⁶. 3 g / mol up to 2.5 × 10 3 Within the range of g / mol.

[0167] 42. The composition according to any one of embodiments 35 to 41, wherein the ratio of polyol (PA) and (PB) is in the range of 9:1 to 1:9.

[0168] 43. The composition according to any one of embodiments 35 to 42, wherein the thermoplastic polyurethane has a content of more than 1.2 × 10⁻⁶ as determined by gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021. 5 The weight-average molecular weight (g / mol) excluding urethane crosslinking.

[0169] 44. The composition according to any one of embodiments 35 to 43, wherein the composition further comprises a thermoplastic resin selected from the group consisting of polystyrene, high-impact polystyrene, polyethylene, polypropylene, polyethylene terephthalate, and thermoplastic elastomers or mixtures thereof.

[0170] 45. The composition according to any one of embodiments 35 to 44, wherein the composition is in pellet form.

[0171] 46. ​​A method for preparing a composition comprising...

[0172] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, and

[0173] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0174] 47. The method according to embodiment 46, wherein the building components of the thermoplastic polyurethane are mixed in a continuous process.

[0175] 48. The method according to any one of embodiments 46 or 47, wherein the building component of the thermoplastic polyurethane is mixed in a device.

[0176] 49. The method according to any one of embodiments 46 to 48, wherein the components are mixed in a reactive extruder.

[0177] 50. The composition according to any one of embodiments 35 to 45 or the composition prepared by any one of embodiments 46 to 48 for use in the production of extruded, injection molded and pressed articles, as well as foams, shoe soles, cable sheaths, hoses, profiles, drive belts, fibers, nonwovens, films, molded articles, plugs, housings, for use in the electrical industry, automotive industry, mechanical engineering, 3D printing, pharmaceutical and consumer products, particularly for use in the production of injection molded products, extruded products, films, profiles and molded articles.

[0178] 51. A molded article comprising a composition according to any one of embodiments 35 to 45 or a composition obtainable or acquireable by any one of embodiments 46 to 50.

[0179] 52. A composition comprising:

[0180] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, wherein the polyol (PA) is selected from the group consisting of polypropylene glycol, and

[0181] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0182] 53. A composition comprising:

[0183] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, wherein the polyol (PA) is selected from the group consisting of polypropylene glycol, and

[0184] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate.

[0185] 54. A composition comprising:

[0186] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, wherein the polyol (PA) is selected from the group consisting of polypropylene glycol, and

[0187] (ii) Component (CC), which is selected from the group of zinc carboxylate.

[0188] 55. The composition according to any one of embodiments 52 to 54, wherein the polyol composition further comprises a polyol (PB) having at least 80% primary terminal hydroxyl groups.

[0189] 56. The composition according to any one of embodiments 52 to 55, wherein the polyol composition (PC) is 100 mol% and the polyol composition contains more than 50 mol% polyol (PA).

[0190] 57. The composition according to any one of embodiments 52 to 56, wherein the polyol (PA) contains more than 94% secondary hydroxyl groups.

[0191] 58. The composition according to any one of embodiments 55 to 57, wherein the polyol (PB) is selected from the group consisting of polyether polyols.

[0192] 59. The composition according to any one of embodiments 52 to 58, wherein the number average molecular weight of the polyol (PA) is 1 × 10⁻⁶. 3 g / mol to 3×10 3 Within the range of g / mol.

[0193] 60. The composition according to any one of embodiments 52 to 59, wherein the number average molecular weight of the polyol (PB) is 0.75 × 10⁻⁶. 3 g / mol up to 2.5 × 10 3 Within the range of g / mol.

[0194] 61. The composition according to any one of embodiments 52 to 60, wherein the ratio of polyol (PA) and (PB) is in the range of 9:1 to 1:9.

[0195] 62. The composition according to any one of embodiments 52 to 61, wherein the thermoplastic polyurethane has a content of more than 1.2 × 10⁻⁶ as determined by gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021. 5 The weight-average molecular weight (g / mol) excluding urethane crosslinking.

[0196] 63. The composition according to any one of embodiments 52 to 62, wherein the composition further comprises a thermoplastic resin selected from the group consisting of polystyrene, high-impact polystyrene, polyethylene, polypropylene and polyethylene terephthalate, and thermoplastic elastomers or mixtures thereof.

[0197] 64. The composition according to any one of embodiments 52 to 63, wherein the composition is in pellet form.

[0198] 65. A method for preparing a composition according to any one of embodiments 52 to 64.

[0199] 66. A method for preparing a composition comprising...

[0200] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, wherein the polyol (PA) is selected from the group consisting of polypropylene glycol, and

[0201] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0202] 67. A method for preparing a composition comprising...

[0203] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, wherein the polyol (PA) is selected from the group consisting of polypropylene glycol, and

[0204] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0205] The method includes the step of reacting at least one diisocyanate (I1), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group and a component (CC) selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably selected from the group consisting of bismuth carboxylate.

[0206] 68. A method for preparing a composition comprising...

[0207] (i) A thermoplastic polyurethane, wherein the thermoplastic polyurethane is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, wherein the polyol (PA) is selected from the group consisting of polypropylene glycol, and

[0208] (ii) Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0209] The method includes the step of mixing the following components: a thermoplastic polyurethane, which is a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) having a secondary hydroxyl group, wherein the polyol (PA) is selected from the group consisting of polypropylene glycol, and

[0210] Component (CC), which is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

[0211] 69. The method according to any one of embodiments 65 to 68, wherein the building components of the thermoplastic polyurethane are mixed in a continuous process.

[0212] 70. The method according to any one of embodiments 65 or 69, wherein the building components of the thermoplastic polyurethane are mixed in a device.

[0213] 71. The method according to any one of embodiments 65 to 70, wherein the components are mixed in a reactive extruder.

[0214] 72. The method according to any one of embodiments 65 to 71, wherein the polyol composition further comprises a polyol (PB) having at least 80% primary terminal hydroxyl groups.

[0215] 73. The method according to any one of embodiments 65 to 72, wherein the polyol composition (PC) is 100 mol% and the content of polyol (PA) in the polyol composition is greater than 50 mol%.

[0216] 74. The method according to any one of embodiments 65 to 73, wherein the polyol (PA) contains more than 94% secondary hydroxyl groups.

[0217] 75. The method according to any one of embodiments 65 to 74, wherein the polyol (PB) is selected from the group consisting of polyether polyols.

[0218] 76. The method according to any one of embodiments 65 to 75, wherein the number-average molecular weight of the polyol (PA) is 1 × 10⁻⁶. 3 g / mol to 3×10 3 Within the range of g / mol.

[0219] 77. The method according to any one of embodiments 65 to 76, wherein the number average molecular weight of the polyol (PB) is 0.75 × 10⁻⁶. 3 g / mol up to 2.5 × 10 3 Within the range of g / mol.

[0220] 78. The method according to any one of embodiments 65 to 77, wherein the ratio of polyol (PA) and (PB) is in the range of 9:1 to 1:9.

[0221] 79. The method according to any one of embodiments 65 to 78, wherein the thermoplastic polyurethane has a viscosity of more than 1.2 × 10⁻⁶ as determined by gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021. 5 The weight-average molecular weight (g / mol) excluding urethane crosslinking.

[0222] 80. The method according to any one of embodiments 65 to 79, wherein the composition further comprises a thermoplastic resin selected from the group consisting of polystyrene, high-impact polystyrene, polyethylene, polypropylene and polyethylene terephthalate, and thermoplastic elastomers or mixtures thereof.

[0223] 81. The method according to any one of embodiments 65 to 31, wherein the composition is in pellet form.

[0224] 82. The composition according to any one of embodiments 52 to 64 or the composition prepared by any one of embodiments 65 to 81 is used for the production of extruded, injection molded and pressed articles, as well as foams, shoe soles, cable sheaths, hoses, profiles, drive belts, fibers, nonwovens, films, molded articles, plugs, housings, for damping elements in the electrical industry, automotive industry, mechanical engineering, 3D printing, pharmaceuticals and consumer products, and particularly for the production of injection molded products, extruded products, films, profiles and molded articles.

[0225] 83. A molded article comprising a composition according to any one of embodiments 52 to 64 or a composition obtainable or acquireable by any one of embodiments 65 to 81.

[0226] The following examples illustrate the present invention. Example

[0227] 1. Determination of molecular weight

[0228] Measurements for determining the molecular weight of urethane esters are performed using GPC according to DIN EN ISO 13885-2:2021. Molecular weights are typically determined using two GPC columns connected in series (column temperature 60°C; flow rate 1 mL / min; RI detector). Calibration is performed using polymethyl methacrylate (PMMA) with DMF as the flow medium. Unlike DIN EN ISO 13885-2:2021, the solvent is generally not mixed with lithium bromide.

[0229] 2. General Procedures

[0230] TPU production was carried out in a Coperion twin-screw extruder ZSK58 MC with a process length of 48D (12 shells). The polyol, diisocyanate, and catalyst were metered into zone 1. The chain extender was metered into zone 3. Additional additives were supplied in zone 8. All TPU was produced at an index of 1000 (Table 1), with only the catalyst varied (Table 2).

[0231] The shell temperature ranges from 160°C to 230°C. Melt discharge and underwater granulation are carried out at melt temperatures ranging from 210°C to 250°C. The screw speed is between 150 L / min and 200 L / min. The production rate ranges from 130 kg / h to 180 kg / h.

[0232] The melt discharge from the extruder is carried out via a gear pump. After melt filtration, the polymer melt is processed into granules by underwater granulation, which are then continuously dried in a heated vortex bed at 40°C to 90°C.

[0233] 3. Materials used

[0234]

[0235] Table 1

[0236]

[0237] (*) Comparative Examples

[0238] 4. Catalysts used

[0239] Use the following catalyst:

[0240] Bismuth neodecanoate

[0241] Tin neodecanoate

[0242] Diisobutoxy-Diacetoethyl Titanate

[0243] Zinc neodecanoate

[0244] Tin 2-ethylhexanoate

[0245] • 0.064 mmol / kg TPU

[0246] • The equimolar amount of all catalysts used is adjusted by the concentration of the catalyst solution.

[0247] Table 2: Catalyst solution concentration in dialkyl esters

[0248] Example

[0249] 5.1 Synthesis Procedure

[0250] TPU production takes place in a twin-screw extruder with a diameter of 92 mm and a length of 56 D. Shell temperatures range from 150°C to 200°C. Screw speeds are between 170 rpm and 200 rpm. Production rates range from 600 kg / h to 900 kg / h. Melt discharge from the extruder is handled by a gear pump. After melt filtration, the polymer melt is processed into granules via underwater granulation, and these granules are continuously dried in a fluidized bed at 40°C to 90°C.

[0251] Table 3

[0252]

[0253] Bismuth neodecanoate, 0.02 mmol / kg TPU

[0254] Table 4

[0255]

[0256] 5.2 Examples with different hardness

[0257] TPU production takes place in a casting process. The components are mixed in a metal container in a one-step process at 90°C. The homogeneous reaction mixture is then poured onto a heated platform and the reaction continues for 10 minutes. The resulting TPU is then heated overnight in an oven at an elevated temperature to complete the conversion.

[0258] Table 5

[0259]

[0260] Bismuth neodecanoate, 0.2 mmol / kg TPU

[0261] Table 6

[0262]

[0263] 5.3 Examples with HDI

[0264] TPU production was carried out in a Coperion twin-screw extruder ZSK58 MC with a process length of 48D (12 shells). The polyol, diisocyanate, and catalyst were metered into zone 1. The chain extender was metered into zone 3. Additional additives were supplied in zone 8. All TPU was produced at an index of 1000 (Table 7), with only the catalyst varied (Table 8).

[0265] The shell temperature ranges from 160°C to 230°C. Melt discharge and underwater granulation are carried out at melt temperatures ranging from 210°C to 250°C. The screw speed is between 150 L / min and 200 L / min. The production rate ranges from 160 kg / h to 210 kg / h.

[0266] The melt discharge from the extruder is carried out via a gear pump. After melt filtration, the polymer melt is processed into granules by underwater granulation, which are then continuously dried in a heated vortex bed at 40°C to 90°C.

[0267] Table 7

[0268]

[0269] Table 8

[0270]

[0271] 6. Sample preparation

[0272] The dried TPU granules are injection molded to obtain an injection molded sheet with a thickness of 2 mm, and the injection molded sheet is tempered at 100°C for 20 hours.

[0273] To determine the molecular weight and solution viscosity excluding urethane, TPU granules were tempered at 110°C for 2 hours and dissolved in a DMF solution containing dialkylamine for 12 hours under constant stirring.

[0274] 7. Testing Methods

[0275] The following measurement methods can be used for material characterization: DSC, DMA, TMA, NMR, FT-IR, GPC.

[0276]

[0277] 8. Results

[0278] The following results demonstrate that bismuth carboxylate and zinc carboxylate-based catalysts allow for the production of TPUs with high solution viscosity (without urethane crosslinking) and high molecular weight. Furthermore, mechanical properties are improved, particularly abrasion resistance and tear resistance.

[0279] Table 8: Analysis

[0280]

[0281] (*) Comparative Examples

[0282] Table 9: Machinery

[0283]

[0284] (*) Comparative Examples

[0285] For tempering and the transparency of injection-molded sheets, transparent materials after injection molding are preferred.

[0286] + = Good transparency

[0287] o = Medium transparency / semi-transparency

[0288] - = Opaque appearance

[0289]

[0290] (*) Comparative Examples

[0291] 9. Processing

[0292] According to Examples 1 to 5, thermoplastic polyurethane was prepared using bismuth neodecanoate as a catalyst and polyol 1: polyol 2 in a ratio of 85:15.

[0293] Processing behavior of dried granules was tested via tube extrusion (3 hours at 100°C).

[0294]

[0295] Processing is carried out in a uniform extrusion tube at an extrusion speed of 16 kg / h to 20 kg / h.

[0296] References :

[0297] WO 02 / 064656A2

[0298] WO 93 / 24549 A1

[0299] US 2006 / 0258831 A1

[0300] EP 1746117 A1

[0301] "Kunststoffhandbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition, 1993, Chapter 3.1

[0302] Kunststoffhandbuch, Volume VII, edited by Vieweg and Höchtlen, Carl HanserVerlag, Munich 1966 (pp. 103-113)

Claims

1. A composition comprising: (i) A thermoplastic polyurethane, said thermoplastic polyurethane being a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), said polyol composition comprising a polyol (PA) having a secondary hydroxyl group, said polyol (PA) being selected from the group consisting of polypropylene glycol, and (ii) Component (CC), wherein the component (CC) is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

2. The composition according to claim 1, wherein the polyol composition further comprises a polyol (PB) having at least 80% primary terminal hydroxyl groups.

3. The composition according to claim 1 or 2, wherein the polyol composition (PC) is 100 mol%, and the content of the polyol (PA) in the polyol composition is greater than 50 mol%.

4. The composition according to any one of claims 1 to 3, wherein the polyol (PA) contains more than 94% secondary hydroxyl groups.

5. The composition according to any one of claims 2 to 4, wherein the polyol (PB) is selected from the group consisting of polyether polyols.

6. The composition according to any one of claims 1 to 5, wherein the number-average molecular weight of the polyol (PA) is 1 × 10⁻⁶. 3 g / mol to 3×10 3 Within the range of g / mol.

7. The composition according to any one of claims 1 to 6, wherein the number average molecular weight of said polyol (PB) is 0.75 × 10⁻⁶. 3 g / mol up to 2.5 × 10 3 Within the range of g / mol.

8. The composition according to any one of claims 1 to 7, wherein the ratio of polyol (PA) and (PB) is in the range of 9:1 to 1:

9.

9. The composition according to any one of claims 1 to 8, wherein the thermoplastic polyurethane has a content of more than 1.2 × 10⁻⁶ m / s, as determined by gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021. 5 The weight-average molecular weight (g / mol) excluding urethane crosslinking.

10. The composition according to any one of claims 1 to 9, wherein the composition further comprises a thermoplastic resin selected from the group consisting of polystyrene, high-impact polystyrene, polyethylene, polypropylene, polyethylene terephthalate, and thermoplastic elastomers or mixtures thereof.

11. The composition according to any one of claims 1 to 10, wherein the composition is in pellet form.

12. A method for preparing a composition, said composition comprising (i) A thermoplastic polyurethane, said thermoplastic polyurethane being a reaction product of at least one diisocyanate (I1), at least one polyol composition (PC), and at least one chain extender (CE), said polyol composition comprising a polyol (PA) having a secondary hydroxyl group, said polyol (PA) being selected from the group consisting of polypropylene glycol, and (ii) Component (CC), wherein the component (CC) is selected from the group consisting of bismuth carboxylate and zinc carboxylate, preferably from the group consisting of bismuth carboxylate.

13. The method of claim 12, wherein the building components of the thermoplastic polyurethane are mixed in a continuous process.

14. The method according to any one of claims 12 or 13, wherein the building components of the thermoplastic polyurethane are mixed in a device.

15. The method according to any one of claims 12 to 14, wherein the components are mixed in a reactive extruder.

16. The composition according to any one of claims 1 to 11 or the composition prepared by the method according to any one of claims 12 to 14 for use in the production of extruded, injection-molded and pressed articles, as well as foams, shoe soles, cable sheaths, hoses, profiles, drive belts, fibers, nonwovens, films, molded articles, plugs, housings, for use in the electrical industry, automotive industry, mechanical engineering, 3D printing, pharmaceuticals and consumer products, particularly for use in the production of injection-molded products, extruded products, films, profiles and molded articles.

17. A molded article comprising a composition according to any one of claims 1 to 11 or a composition obtainable or obtainable by any one of claims 12 to 15.

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