Process for producing thermoplastic polyurethanes

Abstract

The present invention relates to a composition comprising a thermoplastic polyurethane being the 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) with secondary terminal hydroxy groups and further comprising 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 preparing said composition as well as the use of a composition according to the present invention for producing extruded, injection molded and pressed articles and also foams, shoe soles, cable sheathings, hoses, profiles, drive belts, fibers, nonwovens, films, moldings, plugs, housings, damping elements for the electrical industry, automotive industry, mechanical engineering, 3-D printing, medicine and consumer goods, in particular for producing injection molded products, extruded products, films, profiles and shaped articles. The present invention also relates to a shaped article comprising a composition according to the present invention.

Description

[0001] Process for producing thermoplastic polyurethanes

[0002] The present invention relates to a composition comprising a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and further comprising 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 preparing said composition as well as the use of a composition according to the present invention for producing extruded, injection molded and pressed articles and also foams, shoe soles, cable sheathings, hoses, profiles, drive belts, fibers, nonwovens, films, moldings, plugs, housings, damping elements for the electrical industry, automotive industry, mechanical engineering, 3-D printing, medicine and consumer goods, in particular for producing injection molded products, extruded products, films, profiles and shaped articles. The present invention also relates to a shaped article comprising a composition according to the present invention.

[0003] Thermoplastic polyurethane elastomers (TPU) are of great industrial importance on account of their excellent mechanical properties and amenability to cost-effective thermoplastic processing. Variation of the input materials makes it possible to obtain different profiles of properties. The synthesis of the thermoplastically processable polyurethane elastomers may be affected either in stepwise fashion (prepolymer metering method) or by simultaneous reaction of all components in one stage (one-shot metering method). Thermoplastic polyurethanes for various applications are known in principle from the prior art.

[0004] Due to its low cost, polypropylene glycol is an interesting input material for the production of thermoplastic polyurethanes. In the conventional continuous process it is disadvantageous to employ unmodified polypropylene glycol (PPG) since the low reactivity of the secondary OH groups leads to slow molecular weight build-up.

[0005] 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-shot process using polyols having a high proportion of secondary hydroxyl groups. WO 93 / 24549 A1 and US 2006 / 0258831 A1 also disclose one-shot processes for producing thermoplastic polyurethanes using polyols having secondary OH groups. EP 1746117 A1 discloses a process for producing isocyanate-containing prepolymers having a low content of monomeric isocyanates by reaction of diisocyanates with at least one compound having more than two isocyanate-reactive hydrogen atoms and optionally subsequent removal of the unconverted monomeric diisocyanates. A one-shot process using prepolymers is disclosed.

[0006] In the processes known from the prior art it is often difficult to adjust the block lengths and hence the properties of the polymer obtained. It was accordingly an object of the present invention to provide thermoplastic polyurethanes and processes for the production thereof which may employ polypropylene glycol and which exhibit good mechanical properties. It was a further object of the present invention to provide a process for cost-effective production of the corresponding polymers.

[0007] According to the invention this object is achieved by a composition comprising

[0008] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and

[0009] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates preferably from the group consisting of bismuth carboxylates.

[0010] In particular, this object is solved by a composition comprising

[0011] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) is selected from the group of polypropyleneglycols and

[0012] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates preferably from the group consisting of bismuth carboxylates.

[0013] In a further aspect the present invention also provides a process for preparing a composition comprising

[0014] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups, preferably wherein the polyol (PA) is selected from the group of polypropyleneglycols, and

[0015] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates preferably from the group consisting of bismuth carboxylates. The composition according to the present invention comprises a thermoplastic polyurethane and a component (CC) but may also comprise further components. According to the present invention, the thermoplastic polyurethane is the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups.

[0016] It has surprisingly been found that the composition according to the present invention comprising component (CC) and the thermoplastic polyurethanes which are producible using a cost-effective polypropylene glycol having a high proportion of secondary terminal OH groups exhibit good mechanical properties and that transparent products are obtainable. Advantageous properties such as for example low abrasion, higher tensile strength, higher tear propagation resistance, and high softening temperature (TMA onset) can be obtained.

[0017] In the context of the present invention mechanical properties are determined on injection molded plates previously heat treated at 100 °C for 20 h unless otherwise stated.

[0018] The composition comprises a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups. Thermoplastic polyurethanes and processes for their preparation are in principle known. According to the present invention, the polyol composition (PC) comprises a polyol (PA) with secondary hydroxy groups.

[0019] Polyols with secondary hydroxy groups are in principle also known. Polyols with secondary hydroxy groups suitable as polyol (PA) may for example contain more than 85% of secondary hydroxyl groups, for example more than 90% of secondary hydroxyl groups, in particular more than more than 94% of secondary hydroxyl groups, more preferable more than 95% of secondary hydroxyl groups or even up to 100 % of secondary hydroxyl groups. According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the polyol (PA) contains more than 94% secondary hydroxyl groups, preferably more than 98%, in particular more than 99%.

[0020] Suitable are in particular propylene glycols. According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the polyol (PA) is selected from the group of polypropylene glycols. Polypropylene glycols suitable according to the invention include those having a number-average molecular weight Mn in the range from 650 g / mol to 3500 g / mol, in particular a number-average molecular weight Mn in the range from 1000 g / mol to 3000 g / mol, more preferably a number-average molecular weight Mn in the range from 1000 g / mol to 1600 g / mol.

[0021] It has been found that especially polypropylene glycols having higher molecular weights, for example an average molecular weight Mn of more than 3000 or more than 2000, result in less favorable mechanical properties of the obtained thermoplastic polyurethane.

[0022] The employed polyols preferably have a polydispersity Pd of less than 1.4, more preferably less than 1.2.

[0023] According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the number average molecular weight of the polyol (PA) is in the range of from 1000 g / mol to 3000 g / mol.

[0024] In a further embodiment the present invention thus also provides a thermoplastic polyurethane as described hereinabove, wherein the polypropylene glycol has a number-average molecular weight Mn in the range from 1000 g / mol to 1600 g / mol and a polydispersity Pd of less than 1.5.

[0025] The functionality of the propylene glycol preferably is in the range from 1.95 to 2.0, preferably in the range from 1.98 to 2.0.

[0026] Suitable propylene glycols may or example be prepared using DMC catalysts. Suitable processes are known to the person skilled in the art.

[0027] Polyol composition (PC) may comprise further components such as for example further polyols, in particular further polyols with primary hydroxy groups. According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the polyol composition further comprises a polyol (PB) with primary hydroxy groups, in particular a polyol (PB) at least 80% primary hydroxy groups.

[0028] The ratio of the polyols in the polyol composition may vary in broad ranges. Preferably the polyol composition comprises polyol (PA) in an amount of above 50 mol % based on the polyol composition (PC) being 100 mol %. According to a further embodiment, the present invention is also directed to the composition as disclosed above wherein the content of the polyol (PA) in the polyol composition is above 50 mol %, preferably above 70 mol % based on the polyol composition (PC) being 100 mol %, for example in a range of from 50 mol % to 100 mol % based on the polyol composition (PC) being 100 mol %, preferably in a range of from 70 mol % to 95 mol % based on the polyol composition (PC) being 100 mol %.

[0029] Further polyols suitable as polyol (PB) are known in principle to those skilled in the art and described for example in “Kunststoffhandbuch, volume 7, Polyurethane”, Carl Hanser Verlag, 3rd edition 1993, chapter 3.1. Particularly preferably employed as further polyols are polyesterols or polyetherols. According to the invention not only PTHF but also other further polyethers, or else polyesters, are suitable. Particular preference is given to polyether polyols. The number average molecular weight of the polyols employed in accordance with the invention is preferably between 250 g / mol and 2000 g / mol.

[0030] According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the polyol (PB) is selected from the group consisting of polyetherpolyols.

[0031] According to the invention preferred polyetherols are polyethylene glycols and polytetrahydrofurans. Also employable according to the invention are for example mixtures of various polyetherols, for example two or more polytetrahydrofurans differing in molecular weight.

[0032] Suitable examples include a polytetrahydrofuran (PTHF) having a molecular weight Mn in the range from 750 g / mol to 2500 g / mol, more preferably in the range from 800 g / mol to 2000 g / mol, more preferably in the range from 850 g / mol to 1600 g / mol.

[0033] According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the number average molecular weight of the polyol (PB) is in the range of from 0.75 x 103g / mol and 2.5 x 103g / mol.

[0034] It has been found that the thermoplastic polyurethanes have improved properties when the molecular weight or the polarity of polyol (PA) and polyol (PB) are in a similar range.

[0035] Preferably, the molecular weight of polyol (PA) and polyol (PB) is adjusted. Preferably, the molecular weight of polyol (PB) is in the same range or lower than the molecular weight of Polyol (PA). Typically, the molecular weight of polyol (PB) is in the range of from 1000 g / mol above the molecular weight of polyol (PA) to 1000 g / mol below the molecular weight of polyol (PA). The ratio of polyol (PA) and polyol (PB) in the polyol composition may vary in broad ranges, for example in the range of from 9:1 to 1 :9. According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the ratio of polyol (PA) and (PB) is in the range of from 9:1 to 1 :9.

[0036] For the preparation of the thermoplastic polyurethane, a chain extender is used. Suitable are for example chain extenders having a molecular weight < 500 g / mol. In the context of the present invention this is the weight-average molecular weight. Chain extenders used in the context of the present invention may, for example, be compounds having hydroxyl or amino groups, especially having 2 hydroxyl or amino groups. According to the invention, however, it is also possible that mixtures of different compounds are used as chain extenders. According to the invention, the average functionality of the mixture is 2.

[0037] Preference is given in accordance with the invention to using compounds having hydroxyl groups as chain extenders, especially diols. It is preferable to employ aliphatic, araliphatic, aromatic and / or cycloaliphatic diols having a molecular weight of 50 g / mol to 220 g / mol. Preference is given to alkanediols having 2 to 10 carbon atoms in the alkylene radical, especially di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols. Particularly preferred for the present invention are 1 ,2-ethylene glycol, propane-1 , 3-diol, butane-1 ,4-diol, hexane-1 ,6-diol. It is also possible to employ aromatic compounds such as hydroxyquinone bis(2-hydroxyethyl) ether.

[0038] Also employable according to the invention are compounds having amino groups, for example diamines. Likewise employable are mixtures of diols and diamines.

[0039] The chain extender is preferably a diol having a molecular weight Mw < 220 g / mol. According to the invention, it is possible that only one diol having a molecular weight Mw < 220 g / mol is used for preparation of the transparent thermoplastic polyurethane.

[0040] In a further embodiment, more than one diol is used as chain extender. It is thus also possible to employ mixtures of chain extenders.

[0041] The chain extender is preferably employed in an amount such that the molar ratio of the sum of the functionalities of the components of the employed polyol composition (PC) and the chain extender to the sum of the functionalities of the employed diisocyanate (11) is in the range from 1 :0.8 to 1 :1.3, more preferably in the range from 1 :0.9 to 1 :1.2, for example in the range from 1 :0.95 to 1 :1.15. For the preparation of the thermoplastic polyurethane, a diisocyanate (11) is used.

[0042] Suitable diisocyanates are known per se to those skilled in the art. According to the invention at least one diisocyanate is employed. Mixtures of two or more diisocyanates may also be employed according to the invention.

[0043] In the context of the present invention preferred diisocyanates are aliphatic or aromatic diisocyanates, further preferably aromatic diisocyanates.

[0044] Aliphatic diisocyanates employed are customary aliphatic and / or cycloaliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpen- tamethylene 1 ,5-diisocyanate, 2-ethyltetramethylene 1 ,4-diisocyanate, hexamethylene 1 ,6-diiso- cyanate (HDI), pentamethylene 1 ,5-diisocyanate, butylene 1 ,4-diisocyanate, trimethylhexamethylene 1 ,6-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1 ,4- and / or 1 ,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1 ,4-diisocyanate, 1 -methylcyclohexane 2,4- and / or 2, 6-diisocyanate, methylene dicyclohexyl 4,4'-, 2,4'- and / or 2, 2'-diisocyanate (H12MDI).

[0045] Preferred aliphatic diisocyanates are hexamethylene 1 ,6-diisocyanate (HDI), 1-isocyanato- 3,3,5-trimethyl-5-isocyanatomethylcyclohexane and methylene dicyclohexyl 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI); especially preferred are methylene dicyclohexyl 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane or mixtures thereof.

[0046] Suitable aromatic diisocyanates are especially diphenylmethane 2,2'-, 2,4'- and / or 4, 4'-diisocya- nate (MDI), naphthylene 1 ,5-diisocyanate (NDI), tolylene 2,4- and / or 2, 6-diisocyanate (TDI), 3,3’-dimethyl-4,4’-diisocyanatodiphenyl (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'-, 2,4'- and / or 4, 4'-diisocyanate (MDI) and mixtures thereof.

[0047] In a preferred embodiment the diisocyanate (11) is selected from the group consisting of methylenediphenyl diisocyanate (MDI), hexamethylene 1 ,6-diisocyanate (HDI), 1 ,5-naphthylene diisocyanate (NDI), 2,4- and / or 2, 6-tolylene diisocyanate (TDI), 3,3’-dimethyl-4,4'-diisocya- natodiphenyl (TODI), p-phenylene diisocyanate (PDI), 1-isocyanato-3,3,5-trimethyl-5-isocy- anatomethylcyclohexane (isophorone diisocyanate, I PDI) and 4,4'-, 2,4'- and 2,2'-methylenedi- cyclohexyl diisocyanate (H12MDI).

[0048] It is also possible to use mixtures of two or more diisocyanates or use mixtures of diisocyanate (11) and further polyfunctional isocyanates. Preferred examples of polyfunctional isocyanates are triisocyanates, for example triphenylmethane 4,4',4"-triisocyanate, and also the cyanurates of the aforementioned diisocyanates and the oligomers obtainable by partial reaction of diisocyanates with water, for example the biurets of the aforementioned diisocyanates, and oligomers obtainable by specific reaction of semiblocked diisocyanates with polyols having on average more than 2 and preferably 3 or more hydroxyl groups.

[0049] According to the invention the diisocyanate (11) may be used in pure form or in the form of a composition comprising the diisocyanate and at least one solvent. Suitable compatible non-re- active solvents are known to those skilled in the art.

[0050] In a further embodiment the present invention thus also provides a thermoplastic polyurethane as described hereinabove, wherein the diisocyanate (11 )is selected from the group consisting of methylenediphenyl diisocyanate (MDI), hexamethylene 1 ,6-diisocyanate (HDI), 1 ,5-naphthylene diisocyanate (NDI), 2,4- and / or 2, 6-tolylene diisocyanate (TDI), 3,3’-dimethyl-4,4'-diisocya- natodiphenyl (TODI), p-phenylene diisocyanate (PDI), 1-isocyanato-3,3,5-trimethyl-5-isocy- anatomethylcyclohexane (isophorone diisocyanate, I PDI) and 4,4'-, 2,4'- and 2,2'-methylenedi- cyclohexyl diisocyanate (H12MDI).

[0051] The properties of the thermoplastic polyurethanes may vary depending on the ratio of the building components used and the preparation process. The molecular weight of the thermoplastic polyurethane may be determined via GPC. Preferably, the thermoplastic polyurethane has a weight average molecular weight excluding allophanate crosslinking of more than 1.2 x 105g / mol, determined according to gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021.

[0052] The measurement for determining the molecular weight including allophanates is carried out using GPC according to DIN EN ISO 13885-2:2021 , with the TPU dissolved in DMF (0.5% strength). The molecular weight is typically determined using two GPC columns connected in series. Calibration is usually carried out with polymethyl methacrylate, and usually DMF is used as the flow medium. In deviation from DIN EN ISO 13885-2:2021 , the solvents are generally not mixed with lithium bromide, due to system stability, the columns are not run at room temperature, but at elevated temperature for example at 60°C.

[0053] To determine the molecular weight excluding allophanates, the TPU / DMF solution is treated with a secondary amine at elevated temperature to cleave the allophanates.

[0054] According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the thermoplastic polyurethane has a weight average molecular weight excluding allophanate crosslinking of more than 1.2 x 105g / mol, determined according to gel permeation chromatography (GPC) according to EN ISO 13885-2:2021.

[0055] The thermoplastic polyurethane furthermore preferably has a molecular weight Mw including allophanates of more than 150 kD, preferably more than 180 kD, particularly preferably more than 200 kD in the component after tempering for 20 h / 100 °C.

[0056] The ratio of the molecular weight determined with allophanate to without allophanate may for example be in the range of from 2 to 1 to 1 to 1 (measured on the final component after tempering 20 h / 100 °C).

[0057] The composition according to the present invention further comprises a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates preferably from the group consisting of bismuth carboxylates.

[0058] Suitable are for example carboxylates, where the carboxyl radicals independently of one another have 6 to 12 carbon atoms. In the context of the present invention, two or more bismuth carboxylates or zinc carboxylates may be used.

[0059] Suitable bismuth compounds are, in particular, bismuth (2-ethylhexanoate), bismuth octoate and / or bismuth neodecanoate. Preference in accordance with the invention is given to bismuth tri(2-ethylhexanoate), and / or bismuth neodecanoate, more preferably bismuth neodecanoate.

[0060] Suitable zinc compounds are, in particular, zinc 2-ethylhexanoate, zinc octoate and / or zinc neodecanoate. Preference in accordance with the invention is given to zinc 2-ethylhexanoate, and / or zinc neodecanoate.

[0061] According to the present invention, also mixtures of bismuth carboyxlates or zinc carboxylates with further organometallic catalysts such as titanate esters, iron compounds may be used. The composition according to the present invention may for example also comprise titanium organo complexes.

[0062] Suitable are for example mixtures of a bismuth carboxylate or titanium organo complexes such as for example bismuth neodecanoate and titanium(IV)-2-ethylhexyloxide, or bismuth neodecanoate and diisobutoxy-bisethylacetoacetato-titanate.

[0063] It is also possible according to the invention to employ additives or assistants. The composition may also comprise further catalysts. Suitable catalysts are known from the prior art.

[0064] The composition according to the present invention may also comprise further components, such as for example customary auxiliaries. Examples include surface-active substances, fillers, further flame retardants, nucleating agents, oxidation stabilizers, lubricants and mold release assistants, dyes and pigments, optionally stabilizers, to counter hydrolysis, light, heat or discoloration, for example; organic and / or inorganic fillers, reinforcing agents, and plasticizers. Suitable auxiliaries and adjuvants may be found in, for example, Kunststoffhandbuch, volume VII, edited by Vieweg and Hbchtlen, Carl Hanser erlag, Munich 1966 (pp. 103-113).

[0065] The composition according to the present invention may also comprise further 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 in principle known. The polymeric components may be added in suitable amounts.

[0066] According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the composition further comprise a thermoplastic resin selected from the group consisting of polystyrene, high impact polystyrene, polyethylene, polypropylene, and polyethylene terephthalate and thermoplastic elastomers or mixtures thereof.

[0067] In the context of the present invention it is possible to add assistants and / or additives. They may be dissolved in one of the reaction components, preferably in the polyol component or else added in a subsequent mixing apparatus, for example an extruder, once reaction is complete.

[0068] To produce the thermoplastic polyurethanes the synthesis components optionally in the presence of catalysts, assistants and / or additives may be reacted preferably in amounts such that the equivalent ratio of NCO groups to the sum of the NCO-reactive groups, in particular the OH groups, of the low molecular weight compounds and the polyols is 0.9: 1.0 to 1.1 : 1.0, preferably 0.95:1.0 to 1.05:1.0, more preferable 0.97:1.0 to 1.05:1.0,.

[0069] According to the invention the properties of the obtained thermoplastic polyurethanes may be influenced through choice of the employed diisocyanates, polyols and chain extenders. The thermoplastic polyurethane according to the invention advantageously has a Shore hardness in the range from 35 A to 80 D determined according to DIN 53505, more preferably a Shore hardness in the range from 60A to 98A, in each case determined according to DIN 53505.

[0070] In a further embodiment the present invention thus also provides a thermoplastic polyurethane as described hereinabove, wherein the thermoplastic polyurethane has a Shore hardness in the range from 50 A to 80 D determined according to DIN 53505.

[0071] The thermoplastic polyurethanes according to the invention are preferably opaque to transparent. In a further embodiment the present invention thus also provides a thermoplastic polyurethane as described hereinabove, wherein the thermoplastic polyurethane is opaque to transparent. Also thermoplastic polyurethanes with a matt surface can be prepared according to the present invention.

[0072] Typically, the composition according to the present invention is prepared in a suitable form for storage and further processing, for example in form of a powder or a shaped body, in particular in the form of pellets, Thus, according to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the composition is in the form of pellets.

[0073] It has been surprisingly found that the composition according to the present invention has advantageous properties compared to previously known thermoplastic polyurethanes based on polypropyleneglycols. It has been found that the composition according to the present invention has good cold flexibility, low abrasion, and in comparison to previously known thermoplastic polyurethanes based on polypropyleneglycols higher tensile strength, higher tear propagation resistance, lower compression set, higher solution viscosity. In comparison to previously known thermoplastic polyurethanes based on polyethers, the thermoplastic polyurethanes according to the present invention furthermore have a: high softening temperature (TMA onset).

[0074] The composition according to the present invention furthermore has good throughput in extrusion

[0075] According to a further aspect, the present invention is also directed to a process for preparing a composition as disclosed above. According to the present invention, it is possible to prepare the composition from the components, i.e. the thermoplastic polyurethane and the component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates by mixing in a suitable device.

[0076] According to a further embodiment, the composition according to the present invention may be obtained from the preparation process of the thermoplastic polyurethane which preferably is carried out in the presence of the component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0077] The present invention therefore is also directed to a process for preparing a composition comprising

[0078] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and

[0079] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0080] According to one embodiment, the present invention is directed to a process for preparing a composition as disclosed above, the process comprising mixing

[0081] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and

[0082] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0083] According to a further embodiment, the present invention is directed to a process for preparing a composition comprising

[0084] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and

[0085] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates, the process comprising the step of reacting at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups, and a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0086] Suitable preparation processes are in principle known and may comprise mixing steps or further treatment steps. The process of the invention may in particular comprise storage steps and / or heating steps.

[0087] It may be advantageous to run the process as a continuous process, for example as an in-line one-shot process. In a further embodiment the present invention thus also provides a process as described hereinabove, wherein the process is run as a continuous process. According to a further embodiment, the present invention is also directed to the process as disclosed above, wherein the building components of the thermoplastic polyurethane are mixed in a continuous process.

[0088] According to the invention the process is performed such that conversion of the second terminal OH groups of the polypropylene glycol is affected. Temperature and reaction time but also quality of mixing is optimized for example to this end. For example, the reaction may be carried out stepwise. The reaction is preferably run at a temperature in the range of from 160°C to 250°C, preferably in the range of from 180 to 220°C.

[0089] The reaction according to the present invention may per se be carried out in any suitable apparatus known to those skilled in the art

[0090] For example in a process mode in a reactive extruder the reaction duration may be less than 20 min, preferably less than 10 min, in particular less than 5 min, at a reaction temperature of for example in the range from 100°C to 300°C, preferably in the range from 150°C to 250°C, especially in the range from 160°C to 230°C.

[0091] For example in a process mode in a belt process the reaction duration may be less than 30 min, preferably less than 20 min, in particular less than 10 min, for example at a reaction temperature in the range from 100°C to 300°C, preferably in the range from 110°C to 220°C, especially in the range from 120°C to 200°C.

[0092] Typically the temperature during mixing of the prepolymer into the reaction mixture is in the range from 60°C to 300°C, preferably in the range from 70°C to 200°C and particularly preferably in the range from 80°C to 150°C. According to the invention the reaction may be carried out in a suitable apparatus, wherein suitable processes are known per se to those skilled in the art. The mixing of the components is carried out for example with a mixing apparatus, in particular in a mixing apparatus operating with high shear energy. Examples include a mixing head, a static mixer, a nozzle or a multiscrew extruder. According to a further embodiment, the present invention is also directed to the process as disclosed above, wherein the building components of the thermoplastic polyurethane are mixed in one device. Static mixers, reactive extruders or stirred tanks for example are suitable for the reaction according to the present invention.

[0093] According to a further embodiment, the present invention is also directed to the process as disclosed above, wherein the components are mixed in a reaction extruder. Also suitable reactors or a beltline process may be used.

[0094] The temperatures of the extruder housings are advantageously chosen such that the reaction components are completely converted and the possible incorporation of any further assis- tants / the further components may be performed under the gentlest possible conditions for the product.

[0095] The composition according to the present invention is suitable for a wide range of applications. Good mechanical properties and good thermal behavior make the thermoplastic polyurethanes according to the invention suitable in particular for producing extruded, injection molded and pressed articles and also foams, shoe soles, cable sheathings, hoses, profiles, drive belts, fibers, nonwovens, films, moldings, plugs, housings, damping elements for the electrical industry, automotive industry, mechanical engineering, 3-D printing, medicine and consumer goods, in particular for producing injection molded products, extruded products, films, profiles and shaped articles.

[0096] In a further aspect the present invention also provides for the use of a thermoplastic polyurethane according to the invention or of a thermoplastic polyurethane obtainable or obtained by a process according to the invention for producing extruded, injection molded and pressed articles and also foams, shoe soles, cable sheathings, hoses, profiles, drive belts, fibers, nonwovens, films, moldings, plugs, housings, damping elements for the electrical industry, automotive industry, mechanical engineering, 3-D printing, medicine and consumer goods, in particular for producing injection molded products, extruded products, films, profiles and shaped articles. In a further embodiment the present invention thus also provides for the use of a thermoplastic polyurethane according to the invention or of a thermoplastic polyurethane obtainable or obtained by a process according to the invention for producing injection molded products, extruded products, films, profiles and shaped articles as described hereinabove.

[0097] The thermoplastic polyurethanes according to the invention are particularly suitable for producing shaped articles such as extruded, injection molded and pressed articles and also foams, shoe soles, cable sheathings, hoses, profiles, drive belts, fibers, nonwovens, films, moldings, plugs, housings, damping elements for the electrical industry, automotive industry, mechanical engineering, 3-D printing, medicine and consumer goods, in particular for producing injection molded products, extruded products, films, profiles and shaped articles.

[0098] In a further aspect the present invention also provides for a shaped article comprising a composition as disclosed above or a composition obtainable or obtained by a process according to the present invention.

[0099] Further embodiments of the present invention may be found in the claims and the examples. It will be appreciated that the features of the subject matter / processes / uses according to the invention recited above and elucidated below may be used not only in the combination specified in each case but also in other combinations without departing from the scope of the invention. Thus, for example the combination of a preferred feature with a particularly preferred feature or of a not further characterized feature with a particularly preferred feature etc. is also implicitly comprehended even if this combination is not explicitly mentioned.

[0100] Exemplary embodiments of the present invention are recited hereinbelow but are in no way intended to limit the present invention. The present invention especially also comprehends embodiments resulting from the dependency references and thus combinations specified hereinbelow.

[0101] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The composition of any one of embodiments 1 to 4", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The composition* of any one of embodiments 1 , 2, 3 and 4". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.

[0102] 1. A composition comprising

[0103] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and

[0104] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0105] 2. A composition comprising

[0106] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and

[0107] (ii) a component (CC) selected from the group of bismuth carboxylates.

[0108] 3. A composition comprising

[0109] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and

[0110] (ii) a component (CC) selected from the group of zinc carboxylates.

[0111] 4. The composition according to any one of embodiments 1 to 3, wherein the polyol composition further comprises a polyol (PB) with at least 80% primary terminal hydroxy groups.

[0112] 5. The composition according to any one of embodiments 1 to 4, wherein the content of the polyol (PA) in the polyol composition is above 50 mol % based on the polyol composition (PC) being 100 mol %.

[0113] 6. The composition according to any of embodiments 1 to 5, wherein the polyol (PA) contains more than 94% secondary terminal hydroxyl groups. The composition according to any of embodiments 1 to 6, wherein the polyol (PA) is selected from the group of polypropyleneglycols. The composition according to any one of embodiments 4 to 7, wherein the polyol (PB) is selected from the group consisting of polyetherpolyols. The composition according to any of embodiments 1 to 8, wherein the number average molecular weight of the polyol (PA) is in the range of from 1 x 103g / mol to 3 x 103g / mol. The composition according to any of embodiments 1 to 7, wherein the number average molecular weight of the polyol (PB) is in the range of from 0.75 x 103g / mol and 2.5 x 103g / mol. The composition according to any one of embodiments 1 to 10, wherein the ratio of polyol (PA) and (PB) is in the range of from 9:1 to 1 :9. The composition according to any one of embodiments 1 to 11, wherein the thermoplastic polyurethane has a weight average molecular weight excluding allophanate crosslinking of more than 1.2 x 105g / mol, determined according to gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021. The composition according to any of embodiments 1 to 12, wherein the composition further comprise a thermoplastic resin selected from the group consisting of polystyrene, high impact polystyrene, polyethylene, polypropylene, and polyethylene terephthalate and thermoplastic elastomers or mixtures thereof. The composition according to any of the embodiments 1 to 13, wherein the composition is in the form of pellets. A process for preparing a composition according to any of the embodiments 1 to 14. A process for preparing a composition comprising

[0114] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates. A process for preparing a composition comprising

[0115] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and

[0116] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates, the process comprising the step of reacting at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups, and a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates. A process for preparing a composition comprising

[0117] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and

[0118] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates, the process comprising the step of mixing a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups, and a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates. The process according to any one of embodiments 15 to 18, wherein the building components of the thermoplastic polyurethane are mixed in a continuous process. The process according to any one of embodiments 15 or 19, wherein the building components of the thermoplastic polyurethane are mixed in one device. 21. The process according to any one of embodiments 15 to 20, wherein the components are mixed in a reaction extruder.

[0119] 22. The process according to any one of embodiments 15 to 21 , wherein the polyol composition further comprises a polyol (PB) with at least 80% primary terminal hydroxy groups.

[0120] 23. The process according to any one of embodiments 15 to 22, wherein the content of the polyol (PA) in the polyol composition is above 50 mol % based on the polyol composition (PC) being 100 mol %.

[0121] 24. The process according to any one of embodiments 15 to 23, wherein the polyol (PA) contains more than 94% secondary terminal hydroxyl groups.

[0122] 25. The process according to any one of embodiments 15 to 24, wherein the polyol (PA) is selected from the group of polypropyleneglycols.

[0123] 26. The process according to any one of embodiments 15 to 25, wherein the polyol (PB) is selected from the group consisting of polyetherpolyols.

[0124] 27. The process according to any one of embodiments 15 to 26, wherein the number average molecular weight of the polyol (PA) is in the range of from 1 x 103g / mol to 3 x 103g / mol.

[0125] 28. The process according to any one of embodiments 15 to 27, wherein the number average molecular weight of the polyol (PB) is in the range of from 0.75 x 103g / mol and 2.5 x 103g / mol.

[0126] 29. The process according to any one of embodiments 15 to 28, wherein the ratio of polyol (PA) and (PB) is in the range of from 9:1 to 1 :9.

[0127] 30. The process according to any one of embodiments 15 to 29, wherein the thermoplastic polyurethane has a weight average molecular weight excluding allophanate crosslinking of more than 1.2 x 105g / mol, determined according to gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021.

[0128] 31. The process according to any one of embodiments 15 to 30, wherein the composition further comprise a thermoplastic resin selected from the group consisting of polystyrene, high impact polystyrene, polyethylene, polypropylene, and polyethylene terephthalate and thermoplastic elastomers or mixtures thereof.

[0129] 32. The process according to any one of embodiments 15 to 31 , wherein the composition is in the form of pellets.

[0130] 33. The use of a composition according to any of embodiments 1 to 14 or a composition prepared according to the process according to any of embodiments 15 to 32 for producing extruded, injection molded and pressed articles and also foams, shoe soles, cable sheathings, hoses, profiles, drive belts, fibers, nonwovens, films, moldings, plugs, housings, damping elements for the electrical industry, automotive industry, mechanical engineering, 3-D printing, medicine and consumer goods, in particular for producing injection molded products, extruded products, films, profiles and shaped articles.

[0131] 34. A shaped article comprising a composition according to any of embodiments 1 to 14 or a composition obtainable or obtained by a process according to any of embodiments 14 to 32.

[0132] 35. A composition comprising

[0133] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) contains more than 94% secondary terminal hydroxyl groups and

[0134] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0135] 36. The composition according to embodiment 35, wherein the polyol composition further comprises a polyol (PB) with at least 80% primary terminal hydroxy groups.

[0136] 37. The composition according to embodiment 35 or 36, wherein the content of the polyol (PA) in the polyol composition is above 50 mol % based on the polyol composition (PC) being 100 mol %.

[0137] 38. The composition according to any of embodiments 35 to 37, wherein the polyol (PA) is selected from the group of polypropyleneglycols. 39. The composition according to any one of embodiments 36 to 38, wherein the polyol (PB) is selected from the group consisting of polyetherpolyols.

[0138] 40. The composition according to any of embodiments 35 to 39, wherein the number average molecular weight of the polyol (PA) is in the range of from 1 x 103g / mol to 3 x 103g / mol.

[0139] 41. The composition according to any of embodiments 35 to 40, wherein the number average molecular weight of the polyol (PB) is in the range of from 0.75 x 103g / mol and 2.5 x 103g / mol.

[0140] 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 from 9:1 to 1 :9.

[0141] 43. The composition according to any one of embodiments 35 to 42, wherein the thermoplastic polyurethane has a weight average molecular weight excluding allophanate crosslinking of more than 1.2 x 105g / mol, determined according to gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021.

[0142] 44. The composition according to any of embodiments 35 to 43, wherein the composition further comprise a thermoplastic resin selected from the group consisting of polystyrene, high impact polystyrene, polyethylene, polypropylene, and polyethylene terephthalate and thermoplastic elastomers or mixtures thereof.

[0143] 45. The composition according to any of the embodiments 35 to 44, wherein the composition is in the form of pellets.

[0144] 46. A process for preparing a composition comprising

[0145] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups and

[0146] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0147] 47. The process according to embodiment 46, wherein the building components of the thermoplastic polyurethane are mixed in a continuous process. 48. The process according to any one of embodiments 46 or 47, wherein the building components of the thermoplastic polyurethane are mixed in one device.

[0148] 49. The process according to any one of embodiments 46 to 48, wherein the components are mixed in a reaction extruder.

[0149] 50. The use of a composition according to any of embodiments 35 to 45 or a composition prepared according to the process according to any of embodiments 46 to 48 for producing extruded, injection molded and pressed articles and also foams, shoe soles, cable sheathings, hoses, profiles, drive belts, fibers, nonwovens, films, moldings, plugs, housings, damping elements for the electrical industry, automotive industry, mechanical engineering, 3-D printing, medicine and consumer goods, in particular for producing injection molded products, extruded products, films, profiles and shaped articles.

[0150] 51 . A shaped article comprising a composition according to any of embodiments 35 to 45 or a composition obtainable or obtained by a process according to any of embodiments 46 to 50.

[0151] 52. A composition comprising

[0152] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) is selected from the group of polypropyleneglycols and

[0153] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0154] 53. A composition comprising

[0155] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) is selected from the group of polypropyleneglycols and

[0156] (ii) a component (CC) selected from the group of bismuth carboxylates.

[0157] 54. A composition comprising (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) is selected from the group of polypropyleneglycols and

[0158] (ii) a component (CC) selected from the group of zinc carboxylates.

[0159] 55. The composition according to any one of embodiments 52 to 54, wherein the polyol composition further comprises a polyol (PB) with at least 80% primary terminal hydroxy groups.

[0160] 56. The composition according to any one of embodiments 52 to 55, wherein the content of the polyol (PA) in the polyol composition is above 50 mol % based on the polyol composition (PC) being 100 mol %.

[0161] 57. The composition according to any of embodiments 52 to 56, wherein the polyol (PA) contains more than 94% secondary terminal hydroxyl groups.

[0162] 58. The composition according to any one of embodiments 55 to 57, wherein the polyol (PB) is selected from the group consisting of polyetherpolyols.

[0163] 59. The composition according to any of embodiments 52 to 58, wherein the number average molecular weight of the polyol (PA) is in the range of from 1 x 103g / mol to 3 x 103g / mol.

[0164] 60. The composition according to any of embodiments 52 to 59, wherein the number average molecular weight of the polyol (PB) is in the range of from 0.75 x 103g / mol and 2.5 x 103g / mol.

[0165] 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 from 9:1 to 1 :9.

[0166] 62. The composition according to any one of embodiments 52 to 61 , wherein the thermoplastic polyurethane has a weight average molecular weight excluding allophanate crosslinking of more than 1.2 x 105g / mol, determined according to gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021. 63. The composition according to any of embodiments 52 to 62, wherein the composition further comprise a thermoplastic resin selected from the group consisting of polystyrene, high impact polystyrene, polyethylene, polypropylene, and polyethylene terephthalate and thermoplastic elastomers or mixtures thereof.

[0167] 64. The composition according to any of the embodiments 52 to 63, wherein the composition is in the form of pellets.

[0168] 65. A process for preparing a composition according to any of the embodiments 52 to 64.

[0169] 66. A process for preparing a composition comprising

[0170] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) is selected from the group of polypropyleneglycols and

[0171] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0172] 67. A process for preparing a composition comprising

[0173] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) is selected from the group of polypropyleneglycols and

[0174] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates, the process comprising the step of reacting at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups, and a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0175] 68. A process for preparing a composition comprising

[0176] (i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) is selected from the group of polypropyleneglycols and

[0177] (ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates, the process comprising the step of mixing a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) is selected from the group of polypropyleneglycols, and a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

[0178] 69. The process according to any one of embodiments 65 to 68, wherein the building components of the thermoplastic polyurethane are mixed in a continuous process.

[0179] 70. The process according to any one of embodiments 65 or 69, wherein the building components of the thermoplastic polyurethane are mixed in one device.

[0180] 71. The process according to any one of embodiments 65 to 70, wherein the components are mixed in a reaction extruder.

[0181] 72. The process according to any one of embodiments 65 to 71 , wherein the polyol composition further comprises a polyol (PB) with at least 80% primary terminal hydroxy groups.

[0182] 73. The process according to any one of embodiments 65 to 72, wherein the content of the polyol (PA) in the polyol composition is above 50 mol % based on the polyol composition (PC) being 100 mol %.

[0183] 74. The process according to any one of embodiments 65 to 73, wherein the polyol (PA) contains more than 94% secondary terminal hydroxyl groups.

[0184] 75. The process according to any one of embodiments 65 to 74, wherein the polyol (PB) is selected from the group consisting of polyetherpolyols. The process according to any one of embodiments 65 to 75, wherein the number average molecular weight of the polyol (PA) is in the range of from 1 x 103g / mol to 3 x 103g / mol. The process according to any one of embodiments 65 to 76, wherein the number average molecular weight of the polyol (PB) is in the range of from 0.75 x 103g / mol and 2.5 x 103g / mol. The process according to any one of embodiments 65 to 77, wherein the ratio of polyol (PA) and (PB) is in the range of from 9:1 to 1 :9. The process according to any one of embodiments 65 to 78, wherein the thermoplastic polyurethane has a weight average molecular weight excluding allophanate crosslinking of more than 1.2 x 105g / mol, determined according to gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021. The process according to any one of embodiments 65 to 79, wherein the composition further comprise a thermoplastic resin selected from the group consisting of polystyrene, high impact polystyrene, polyethylene, polypropylene, and polyethylene terephthalate and thermoplastic elastomers or mixtures thereof. The process according to any one of embodiments 65 to 31 , wherein the composition is in the form of pellets. The use of a composition according to any of embodiments 52 to 64 or a composition prepared according to the process according to any of embodiments 65 to 81 for producing extruded, injection molded and pressed articles and also foams, shoe soles, cable sheathings, hoses, profiles, drive belts, fibers, nonwovens, films, moldings, plugs, housings, damping elements for the electrical industry, automotive industry, mechanical engineering, 3-D printing, medicine and consumer goods, in particular for producing injection molded products, extruded products, films, profiles and shaped articles. A shaped article comprising a composition according to any of embodiments 52 to 64 or a composition obtainable or obtained by a process according to any of embodiments 65 to 81. The following examples illustrate the invention.

[0185] Examples

[0186] 1. Determination of the molecular weight

[0187] The measurement for determining the molecular weight including allophanates is carried out using GPC according to DIN EN ISO 13885-2:2021. The molecular weight is typically determined using two GPC columns connected in series (; column temperature 60°C; flow 1 mL / min; Rl detector). Calibration is carried out with polymethyl methacrylate, DMF is used as the flow medium. In deviation from DIN EN ISO 13885-2:2021 , the solvents are generally not mixed with lithium bromide.

[0188] 2. General procedure

[0189] The production of the TPUs was carried out in a twin-screw extruder, ZSK58 MC, of the company Coperion with a process length of 48D (12 housings). Polyol, diisocyanate and catalyst were dosed into the first zone. The chain extender was dosed in zone 3. The supply of further additives takes place in zone 8. All TPUs were produced with an index of 1000 (table 1), only the catalyst was varied (table 2).

[0190] The housing temperatures are in the range 160 - 230 °C. The melt discharge and underwater pelletizing are carried out at melt temperatures of 210 - 250°C. The screw speed is between 150 and 200 1 / min. The throughput is in the range of 130 - 180 kg / h.

[0191] The melt discharge from the extruder was carried out by a gear pump. After melting filtration, the polymer melt was processed by underwater granulation into granules, which were continuously dried in a heating vortex bed, at 40 - 90 ° C.

[0192] 3. Materials used

[0193] Polyoll Polypropyleneglycole with sec. OH groups and a functionality of 1.98

[0194] (secondary OH groups), OH number 78

[0195] Polyol2 Polytetrahydrofurane 1000 with a functionality of 2.0 (primary OH grous),

[0196] OH number 113.4 Isocyanat 1 4,4’- Methylendiphenylisocyanate (4,4’-MDI)

[0197] Isocyanat 2 Hexamethylene diisocyanate

[0198] Chain extender 1 1 ,4-Butanediol

[0199] Chain extender 21 ,6-Hexanediol

[0200] Chain extender 31 ,2-Propanediol

[0201] Additiv 1 Sterically hindered phenol

[0202] Additiv 2 Hindered amine light stabilizer

[0203] Additiv 3 UV absorber

[0204] Table 1

[0205] (*) comparative example

[0206] 4. Catalyst used

[0207] The following catalysts were used

[0208] Bi-neodecanoat

[0209] Sn-neodecanoat

[0210] Diisobutoxy-bisethylacetoacetatotitanate

[0211] Zn-neodecanoate

[0212] Sn- 2-Ethylhexanoate

[0213] 0.064 mmol per kg of TPU

[0214] Equimolar amount used for all catalysts adjusted via catalyst solution concentration. Table 2: Catalyst solution concentrations in Dialkylester 5. Examples

[0215] 5.1 Synthesis procedure

[0216] The production of the TPUs was carried out in a twin-screw extruder with a diameter of 92 mm and a length of 56D. The housing temperatures are in the range 150 - 200 °C.

[0217] The screw speed was between 170 and 200 1 / min. The throughput was in the range of 600 - 900 kg / h. The melt discharge from the extruder was carried out by a gear pump. After melt filtration, the polymer melt was processed by underwater granulation into granules, which were continuously dried in a fluidized-bed dryer, at 40 - 90 ° C.

[0218] Table 3 Bi neodeanoate, 0.02 mmol per kg of TPU

[0219] Table 4

[0220] 5.2 Examples with varying hardness

[0221] The production of the TPUs was carried out in a casting procedure. The ingredients were mixed as a one-shot approach in a metal container at a temperature of 90 °C. Subse- quently, the homogeneous reaction mixture was poured onto a heating table to continue reacting for 10 minutes. The resulting TPU was heated overnight in a heating oven at elevated temperature to complete the conversion.

[0222] Table 5

[0223] Bi neodeanoate, 0.2 mmol per kg of TPU

[0224] Table 6

[0225] 5.3 Examples with H DI

[0226] The production of the TPUs was carried out in a twin-screw extruder, ZSK58 MC, of the company Coperion with a process length of 48D (12 housings). Polyol, diisocyanate and catalyst were dosed into the first zone. The chain extender was dosed in zone 3. The supply of further additives takes place in zone 8. All TPUs were produced with an index of 1000 (table 7), only the catalyst was varied (table 8).

[0227] The housing temperatures are in the range 160 - 230 °C. The melt discharge and underwater pelletizing are carried out at melt temperatures of 210 - 250°C. The screw speed is between 150 and 200 1 / min. The throughput is in the range of 160 - 210 kg / h.

[0228] The melt discharge from the extruder was carried out by a gear pump. After melting filtration, the polymer melt was processed by underwater granulation into granules, which were continuously dried in a heating vortex bed, at 40 - 90 ° C.

[0229] Table 7 Table 8

[0230] 6. Preparation of the samples

[0231] The dried TPU granules were processed via injection molding to obtain injection molded plates with a thickness of 2 mm, which were tempered for 20 h at 100 °C.

[0232] To determine the molecular weight and solution viscosity excluding allophanates, the TPU granules were tempered at 110°C for 2h and dissolved for 12 h with constant agitation in a DMF solution with a dialkylamine.

[0233] 7. Testing Method

[0234] The following measurement methods can be used for material characterization: DSC, DMA, TMA, NMR, FT-IR, GPC

[0235] Density DIN EN ISO 1183-1 :2019-09, procedure A

[0236] Shore A hardness DIN ISO 48-4:2021-02 (average value; indentation of 3s)

[0237] Tensile strength DIN 53504:2017-03, test specimen S2, testing speed 200mm / min

[0238] Elongation at break DIN 53504:2017-03, test specimen S2, testing speed 200mm / min

[0239] Tear resistance DIN ISO 34-1 , procedure B, method (b): 2016-09

[0240] Abrasion DIN ISO 4649:2021-06, procedure A, standard reference Elastomer No.1

[0241] 8. Results The following results demonstrate that the catalysts based on Bi-carboxylates and Zn-car- boxylates allow to produce TPU with high solution viscosity (without allophanate crosslinking) and high molecular weights. Additionally, mechanical performance is improved, in particular abrasion and tear resistance.

[0242] Table 8: Analytics

[0243] (*) comparative example

[0244] Table 9: Mechanics (*) comparative example

[0245] Transparency of tempered and injection molded plates, preferred is a transparent material after injection molding.

[0246] + = good transparency o = medium transparency I translucent

[0247] - = Opaque appearance Example Transparency

[0248] (*) comparative example

[0249] 9. Processing

[0250] A thermoplastic polyurethane was prepared in accordance with examples 1 to 5 using Bi neodecanoate as a catalyst, polyol 1:polyol2 85:15.

[0251] The processing behavior of the dried granules (3 h at 100 °C) was tested via extrusion of tubes.

[0252] Conditions: Temperatures in the different zones of the extruder between 150-200 °C

[0253] Extruder size 45mm by “Arenz”, 3-zone screw with ratio 1:2.5 Diameter nozzle: 6.9 mm

[0254] Diameter mandrel: 10.3 mm

[0255] Processing yielded in a homogeneous extruded tube with extrusion speed of 16-20 kg / h.

[0256] Literature cited:

[0257] WO 02 / 064656A2

[0258] WO 93 / 24549 A1

[0259] US 2006 / 0258831 A1

[0260] EP 1746117 A1

[0261] “Kunststoffhandbuch, volume 7, Polyurethane”, Carl Hanser Verlag, 3rd edition 1993, chapter 3.1.

[0262] Kunststoffhandbuch, volume VII, edited by Vieweg and Hdchtlen, Carl Hanser erlag, Munich 1966 (pp. 103-113)

Claims

Claims1. A composition comprising(i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) is selected from the group of polypropyleneglycols and(ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

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

3. The composition according to claim 1 or 2, wherein the content of the polyol (PA) in the polyol composition is above 50 mol % based on the polyol composition (PC) being 100 mol %.

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

6. The composition according to any of claims 1 to 5, wherein the number average molecular weight of the polyol (PA) is in the range of from 1 x 103g / mol to 3 x 103g / mol.

7. The composition according to any of claims 1 to 6, wherein the number average molecular weight of the polyol (PB) is in the range of from 0.75 x 103g / mol and 2.5 x 103g / 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 from 9:1 to 1:9.

9. The composition according to any one of claims 1 to 8, wherein the thermoplastic polyurethane has a weight average molecular weight excluding allophanate crosslinking of morethan 1.2 x 105g / mol, determined according to gel permeation chromatography (GPC) according to DIN EN ISO 13885-2:2021.

10. The composition according to any of claims 1 to 9, wherein the composition further comprise a thermoplastic resin selected from the group consisting of polystyrene, high impact polystyrene, polyethylene, polypropylene, and polyethylene terephthalate and thermoplastic elastomers or mixtures thereof.11 . The composition according to any of the claims 1 to 10, wherein the composition is in the form of pellets.

12. A process for preparing a composition comprising(i) a thermoplastic polyurethane being the reaction product of at least one diisocyanate (11), at least one polyol composition (PC) and at least one chain extender (CE), wherein the polyol composition comprises a polyol (PA) with secondary terminal hydroxy groups wherein the polyol (PA) is selected from the group of polypropyleneglycols and(ii) a component (CC) selected from the group of bismuth carboxylates and zinc carboxylates, preferably from the group consisting of bismuth carboxylates.

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

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

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

16. The use of a composition according to any of claims 1 to 11 or a composition prepared according to the process according to any of claims 12 to 14 for producing extruded, injection molded and pressed articles and also foams, shoe soles, cable sheathings, hoses, profiles, drive belts, fibers, nonwovens, films, moldings, plugs, housings, damping elements for the electrical industry, automotive industry, mechanical engineering, 3-D printing, medicine and consumer goods, in particular for producing injection molded products, extruded products, films, profiles and shaped articles.

17. A shaped article comprising a composition according to any of claims 1 to 11 or a composition obtainable or obtained by a process according to any of claims 12 to 15.

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