Process for preparing polyether-containing thermoplastic polyurethanes

Abstract

The present invention relates to processes for preparing polyether-containing thermoplastic polyurethanes and polyether-containing thermoplastic polyurethanes obtained or obtainable by these processes. The present invention further relates to uses of these polyether-containing thermoplastic polyurethanes and articles containing or consisting of the polyether-containing thermoplastic polyurethanes. The present invention further relates to the use of a C3 polyether homopolymer polyol in combination with a C2 polyether homopolymer polyol and / or a C2 / C3 polyether block copolymer polyol and / or a C4 polyether homopolymer polyol, preferably the use of a C3 polyether homopolymer polyol in combination with a C2 / C3 polyether block copolymer polyol, to enhance the low-temperature impact strength and / or tensile strength of the polyether-containing thermoplastic polyurethanes.

Description

[Technical Field]

[0001] The present invention relates to processes for preparing polyether-containing thermoplastic polyurethanes and polyether-containing thermoplastic polyurethanes obtained or obtainable by these processes. The present invention further relates to uses of these polyether-containing thermoplastic polyurethanes and articles containing or consisting of the polyether-containing thermoplastic polyurethanes. The present invention further relates to the use of a C3 polyether homopolymer polyol in combination with a C2 polyether homopolymer polyol and / or a C2 / C3 polyether block copolymer polyol and / or a C4 polyether homopolymer polyol, preferably the use of a C3 polyether homopolymer polyol in combination with a C2 / C3 polyether block copolymer polyol, to enhance the low-temperature impact strength and / or tensile strength of the polyether-containing thermoplastic polyurethanes. [Background technology]

[0002] Conventional technology Thermoplastic polyurethanes (TPUs) have been known for some time. They are of great industrial importance because they combine the known advantages of cost-effective thermoplastic processability with advanced mechanical properties. The use of different chemical building blocks allows for a wide variation in mechanical properties. An overview of TPUs, their properties, and applications can be found, for example, in Kunststoffe 68 (1978), pp. 819-825, or Kautschuk and Gummi, Kunststoffe 35 (1982), pp. 568-584. TPUs are formed from linear polyols (usually polyethers or polyesters), organic diisocyanates, and short-chain diols (chain extenders). TPUs are typically produced without solvents and can be produced continuously or batchwise. The best known industrial preparation processes, which are also used industrially, are the belt process (GB 1057018A) and the extruder process (DE 1964834A-1 and DE 2059570A-1).

[0003] To tailor the properties, the components can be varied within a relatively wide molar ratio range. Macrodiol to chain extender molar ratios of 1:1 to 1:12 have proven useful. The hardness of the TPU can be adjusted within a wide range via the amount of chain extender. This results in products with a hardness range of about 40 Shore A to about 85 Shore D.

[0004] To improve processing behavior, especially cycle time, TPUs with a very high solidification rate after processing in injection molded articles are particularly interesting across the entire hardness range from about 40 Shore A to about 85 Shore D. In particular, in the case of hard and soft TPUs, the polarity difference between these phases is so large that problems often arise in the chemical bonding between the hard and soft segments. As a result, the overall potential of mechanical and processing properties is often not fully utilized. Numerous attempts have been made to overcome these drawbacks in specific ways.

[0005] A process for preparing thermoplastically processable polyurethanes is described by W. Brauer et al. (EP-A 1757632). The homogeneity of the TPU is improved by a multi-stage OH-prepolymer process. However, this improved homogeneity slows down the solidification rate of the TPU.

[0006] A process for preparing low-shrinkage, flexible, easily demoldable thermoplastic polyurethane elastomers has been described by W. Brauer et al. (EP-A 1338614). Pre-stretching the soft segments improved the demolding behavior of TPUs between 45 Shore A and 65 Shore A. At very high hardnesses, this process has obvious drawbacks. Incompatibility develops between the hard and soft phases, and good bonding between these phases no longer occurs. As a result, the high molecular weight of the TPU required for good mechanical properties is not achieved. In fact, the process is highly unstable due to excessively high and fluctuating viscosities in the prepolymer stage, and it no longer functions satisfactorily below 60 Shore A. This means frequent extruder downtime.

[0007] For example, to improve the low-temperature impact strength of polyester-based TPUs for ski boots, polyether polyols with molecular weights greater than 1600 g / mol, such as polytetramethylene ether glycol (US Pat. No. 4,980,445 A) and polypropylene diol ether (WO / 2018 / 158327), are used as modifiers. Because the hard and soft phases in TPUs are incompatible, resulting in insufficient bonding between these phases, it is difficult to incorporate such polyethers as a pure soft phase into TPUs with hardnesses greater than 60 Shore D. It is difficult to prepare hard TPUs with excellent low-temperature impact strength without using modifiers.

[0008] The use of polypropylene glycol or poly(propylene oxide) homopolymers (hereinafter also referred to as C3 polyether homopolymer polyols) as polyol components in the preparation of thermoplastic polyurethanes is of interest, particularly because of their low cost as starting materials. The use of polypropylene glycol in the preparation of thermoplastic polyurethanes is known, for example, from WO 2020 / 109566 A1, in which a polyol based on polypropylene glycol is reacted with a polyisocyanate.

[0009] However, a disadvantage associated with using polypropylene glycol as a polyol component is that thermoplastic polyurethanes with sufficient mechanical properties and abrasion resistance can only be synthesized with relatively low Shore A or theoretical hardness. Rigid thermoplastic polyurethanes based on polypropylene glycol usually exhibit these typical properties to a small extent, if at all, and are therefore not suitable for applications requiring harder materials. Furthermore, this type of thermoplastic polyurethane exhibits low low-temperature impact strength, making it impossible to use it in articles exposed to low temperatures. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] GB 1057018A [Patent Document 2] DE 1964834A-1 [Patent Document 3] DE 2059570A-1 [Patent Document 4] EP-A 1757632 [Patent Document 5] EP-A 1338614 [Patent Document 6] US4980445A [Patent Document 7] WO 2018 / 158327 [Patent Document 8] WO 2020 / 109566 A1 [Non-patent literature]

[0011] [Non-Patent Document 1] Kunststoffe 68 (1978), pages 819 to 825 [Non-patent document 2] Kautschuk, Gummi, Kunststoffe 35 (1982), pages 568 to 584 Summary of the Invention [Problem to be solved by the invention]

[0012] The problem addressed by the present invention was therefore to provide a process for preparing polyether-containing thermoplastic polyurethanes with improved mechanical properties, in particular polyether-containing thermoplastic polyurethanes with increased hardness or increased tensile strength and / or low-temperature impact strength. In particular, the objective is to provide a cost-effective process for preparing polyether-containing thermoplastic polyurethanes with an improved CO balance. [Means for solving the problem]

[0013] The object of the present invention is to provide a composition comprising or consisting of the following components: (A) at least one polyether homopolymer polyol; (B) at least one polyisocyanate; (C) at least one chain extender; (D) optionally, a catalyst; (E) optionally, at least one additive, auxiliary and / or additive; The problem is solved by a process for preparing a polyether-containing thermoplastic polyurethane by reacting The polyether homopolymer polyol is a C3 polyether homopolymer polyol (A1), and component (A) further comprises at least one component (A2), wherein component (A2) comprises or consists of a C2 polyether homopolymer polyol and / or a C2 / C3 polyether block copolymer polyol and / or a C4 polyether homopolymer polyol, and wherein the mass ratio of component (A1) to component (A2) is 95:5 to 25:75 based on the total mass of component (A1) and component (A2).

[0014] The present invention further relates to a polyether-containing thermoplastic polyurethane obtained or obtainable by the process according to the invention.

[0015] The present invention further relates to the use of the polyether-containing thermoplastic polyurethanes according to the invention for producing: injection-molded articles; extruded articles; pressed articles; compression-molded articles; 3D-printed articles; products for mechanical engineering, road construction and railway construction; medical and dental products, in particular aligners for treating crooked teeth; shoes, in particular ski boots; products for the automotive industry; products for the electrical industry, in particular cable sheaths, housings and plug connectors; consumer products; coatings; hoses; profiles; belts; films; fibers; nonwovens; woven fabrics; damping elements; sealing elements.

[0016] The present invention further relates to an article comprising or consisting of the polyether-containing thermoplastic polyurethane according to the invention, wherein the article is preferably a ski boot.

[0017] The present invention finally relates to the use of a C3 polyether homopolymer polyol in combination with a C2 polyether homopolymer polyol and / or a C2 / C3 polyether block copolymer polyol and / or a C4 polyether homopolymer polyol for increasing the Charpy impact strength and / or tensile strength of a polyether-containing thermoplastic polyurethane, in particular for increasing the Charpy impact strength and / or tensile strength of a polyether-containing thermoplastic polyurethane according to the invention (wherein the low-temperature impact strength is measured in particular as the Charpy impact strength).

[0018] Surprisingly, it has been found that when the polyether homopolymer polyol in the preparation of polyether-containing thermoplastic polyurethanes is a C3 polyether homopolymer polyol, the mechanical properties of these polyurethanes (in particular the hardness or tensile strength and / or low-temperature impact strength) can be improved by additionally using a C2 polyether homopolymer polyol and / or a C2 / C3 polyether block copolymer polyol and / or a C4 polyether homopolymer polyol together with the C3 polyether homopolymer polyol.

[0019] In the context of the present invention, a C2 polyether homopolymer polyol is understood to be a polyol based on polyethylene glycol or poly(ethylene oxide), a C3 polyether homopolymer polyol is understood to be a polyol based on polypropylene glycol or poly(propylene oxide), a C2 / C3 polyether block copolymer polyol is understood to be a polyol based on polyethylene glycol or poly(ethylene oxide) and polypropylene glycol or poly(propylene oxide), and a C4 polyether homopolymer polyol is understood to be a polyol based on polytetramethylene glycol. The "C" in "C2," "C3," etc., represents a carbon atom, and the following number represents the number of carbon atoms in the repeat unit of the respective polymer. DETAILED DESCRIPTION OF THE INVENTION

[0020] Particularly preferably, the polyether homopolymer polyol is a C3 polyether homopolymer polyol (A1).

[0021] The process according to the present invention can be carried out batchwise or continuously, whereby a continuous process regime is preferred, especially on an industrial scale (for example, as an in-line one-shot process).Furthermore, it is also preferred that the process is carried out without solvent.Examples of possible further synthesis processes include those known as prepolymer process, MDI splitting or three-stage equivalent prepolymer process, which are generally known to those skilled in the art.

[0022] In the process according to the invention, preferably The C2 polyether homopolymer polyol has a number average molecular weight in the range of 500 to 4000 g / mol, preferably in the range of 1000 to 3000 g / mol; The C3 polyether homopolymer polyol has a number average molecular weight in the range of 500 to 8000 g / mol, preferably in the range of 1000 to 4500 g / mol; The C2 / C3 polyether block copolymer polyol has a number average molecular weight in the range of 1000 to 4000 g / mol, preferably in the range of 1500 to 2500 g / mol; and / or The C4 polyether homopolymer polyol has a number average molecular weight in the range of 500 to 4500 g / mol, preferably in the range of 1500 to 4500 g / mol.

[0023] In a further embodiment of the process according to the invention, the polyether-containing thermoplastic polyurethane has a theoretical hardness of 40% or more, wherein the theoretical hardness is calculated by the following formula: Theoretical hardness = (n (chain extender) × M (polyisocyanate) + m (chain extender)) / m 総量 where: n = molar amount of component, M = molar mass of component, and m = mass of component.

[0024] In the context of the present invention, it is also preferred that the molar ratio of ethylene oxide units to propylene oxide units in the C2 / C3 polyether block copolymer polyol is from 95:5 to 5:95, preferably from 80:20 to 20:80, based on the molar amount of alkylene oxide used in preparing the polyether.

[0025] Furthermore, the mass ratio of component (A1) to component (A2) is preferably 65:35 to 30:70 based on the total mass of component (A1) and component (A2).

[0026] Furthermore, preferably, the polyisocyanate of component (B) comprises or consists of diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 2,2'-diisocyanate, hexamethylene 1,6-diisocyanate, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, isophorone diisocyanate, naphthylene 1,5-diisocyanate, 1,1'-methylenebis(4-isocyanatocyclohexane) or a mixture thereof, and preferably comprises or consists of diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 2,2'-diisocyanate or a mixture thereof.

[0027] Preferably, the chain extender of component (C) is selected from the group comprising or consisting of ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 1,4-di(β-hydroxyethyl)hydroquinone, triethylene glycol, tetraethylene glycol or mixtures thereof, preferably selected from the group comprising or consisting of ethane-1,2-diol, butane-1,4-diol, hexane-1,6-diol, triethylene glycol or mixtures thereof.

[0028] Usable catalysts (D) include conventional catalysts known in polyurethane chemistry. Suitable catalysts are conventional tertiary amines known per se, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane, etc., and also, in particular, organometallic compounds, such as titanium esters, iron compounds, bismuth compounds, tin compounds, such as tin diacetate, tin dioctoate, tin dilaurate, or dialkyltin salts of aliphatic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, etc. Preferred catalysts are organometallic compounds, in particular titanium esters, iron compounds, or tin compounds. Very particular preference is given to dibutyltin dilaurate, tin dioctoate, and titanium esters.

[0029] Additives, auxiliaries, and additives (E) that can be used include, for example, lubricants, such as fatty acid esters, their metal soaps, fatty acid amides, and silicon compounds; antiblocking agents; inhibitors; stabilizers against hydrolysis, light, heat, and discoloration; flame retardants; dyes; pigments; inorganic or organic fillers; nucleating and reinforcing agents; and monofunctional chain terminators. Reinforcing agents are, in particular, fibrous reinforcing materials, such as inorganic fibers, which can be prepared and sized according to the prior art. Monofunctional chain terminators can be, for example, monoalcohols, such as 1-butanol, 1-hexanol, 1-octanol, and stearyl alcohol, or monoamines, such as 1-butylamine and stearylamine, to set a specific TPU molecular weight. Further details about the auxiliaries and additives mentioned here can be found in the specialist literature, for example in J.H. Saunders, K.C. Frisch: "High Polymers", volume XVI, Polyurethanes, parts 1 and 2, Interscience Publishers 1962 and 1964, R. Gachter, H. Müller (eds.): Taschenbuch der Kunststoff-Additive [Handbook of Plastics Additives], 3rd edition, Hanser Verlag, Munich 1989 or DE-A 29 01 774.

[0030] Furthermore, preferably, the process comprises or consists of the following steps: (i) reacting a mixture comprising all of component (A), a portion of component (B), and optionally some or all of component (D) and / or component (E) to form an NCO-functional prepolymer, wherein the molar ratio of component (B) (in part) to component (A) is in the range of 1.1:1.0 to 5.0:1.0; (ii) reacting the NCO-functional prepolymer from step (i) with the entire amount of component (C), optionally in the presence of a further portion or remainder of component (D) and / or component (E), to form an OH-functional prepolymer; (iii) reacting the OH-functional prepolymer from step (ii) with the remaining amount of component (B) and, if applicable, with the remaining amount of component (D) and / or component (E) to form a polyether-containing thermoplastic polyurethane; Here, in step (ii), preferably the molar ratio of NCO functional groups to OH functional groups in component (C) is less than 1.0.

[0031] The reaction is preferably carried out with an isocyanate index of 0.9 to 1.2, more preferably 0.95 to 1.1, and particularly preferably 0.97 to 1.03. The isocyanate index (also referred to as index or NCO / OH index) is understood here to mean the quotient of the molar amount [mol] of isocyanate groups actually used and the molar amount [mol] of isocyanate-reactive groups actually used. That is, this index indicates the ratio (%) of the amount of isocyanate actually used to the stoichiometric amount of isocyanate, i.e., the amount calculated to convert OH equivalents. The equivalent of NCO groups and NCO-reactive hydrogen atoms corresponds here to an NCO / OH index of 1. The isocyanate index is calculated here by the following formula: Index = [(moles of isocyanate groups) / (moles of isocyanate reactive groups)].

[0032] The polyether-containing thermoplastic polyurethane according to the present invention preferably comprises a tensile strength, measured according to ISO 53504 (2009-10), of at least 17 MPa, preferably at least 22 to 60 MPa; and / or At least 30 KJ / m measured at -20°C according to DIN EN ISO179 / 1eA(2010) 2 , preferably 50 to 140 KJ / m 2 Charpy impact strength; It has the following characteristics.

[0033] The Charpy impact strength measured at -20°C according to DIN EN ISO 179 / 1eA (2010) is understood in the context of the present invention as a measure of low-temperature impact strength. Charpy impact strength tests are carried out on injection-molded test specimens at -20°C according to DIN EN ISO 179 / 1eA (2010). The test specimens have the following dimensions: length 80±2 mm, width 10.0±0.2 mm, and thickness 4.0±0.2 mm. The test specimens are notched. The radius rN of the notch base is 0.25±0.05 mm.

[0034] Embodiment The present invention particularly relates to the following embodiments:

[0035] In a first embodiment, the present invention provides a composition comprising or consisting of the following components: (A) at least one polyether homopolymer polyol; (B) at least one polyisocyanate; (C) at least one chain extender; (D) optionally, a catalyst; (E) optionally, at least one additive, auxiliary and / or additive; 1. A process for preparing a polyether-containing thermoplastic polyurethane by reacting The polyether homopolymer polyol is a C3 polyether homopolymer polyol (A1), and component (A) further comprises at least one component (A2), wherein component (A2) comprises or consists of a C2 polyether homopolymer polyol and / or a C2 / C3 polyether block copolymer polyol and / or a C4 polyether homopolymer polyol, and wherein the mass ratio of component (A1) to component (A2) is 95:5 to 25:75 based on the total mass of component (A1) and component (A2).

[0036] In a second embodiment, the present invention provides a method for manufacturing a semiconductor device comprising: The C2 polyether homopolymer polyol has a number average molecular weight in the range of 500 to 4000 g / mol, preferably in the range of 1000 to 3000 g / mol; The C3 polyether homopolymer polyol has a number average molecular weight in the range of 500 to 8000 g / mol, preferably in the range of 1000 to 4500 g / mol; The C2 / C3 polyether block copolymer polyol has a number average molecular weight in the range of 1000 to 4000 g / mol, preferably in the range of 1500 to 2500 g / mol; and / or The C4 polyether homopolymer polyol has a number average molecular weight in the range of 500 to 4500 g / mol, preferably in the range of 1500 to 4500 g / mol; 2. The process of embodiment 1, characterized in that

[0037] In a third embodiment, the present invention relates to the process of embodiment 1 or 2, wherein the theoretical hardness of the polyether-containing thermoplastic polyurethane is 40% or more, wherein the theoretical hardness is calculated by the following formula: Theoretical hardness = (n (chain extender) × M (polyisocyanate) + m (chain extender)) / m 総量 where: n = molar amount of component, M = molar mass of component, and m = mass of component.

[0038] In a fourth embodiment, the invention relates to the process of any of the preceding embodiments, wherein the molar ratio of ethylene oxide units to propylene oxide units in the C2 / C3 polyether block copolymer polyol is from 95:5 to 5:95, preferably from 80:20 to 20:80, based on the molar amount of alkylene oxide used in preparing the polyether.

[0039] In a fifth embodiment, the invention relates to the process of any of the preceding embodiments, wherein the mass ratio of component (A1) to component (A2), based on the combined mass of component (A1) and component (A2), is from 65:35 to 30:70.

[0040] In a sixth embodiment, the invention relates to the process of any of the preceding embodiments, wherein the polyisocyanate of component (B) comprises or consists of diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 2,2'-diisocyanate, hexamethylene 1,6-diisocyanate, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, isophorone diisocyanate, naphthylene 1,5-diisocyanate, 1,1'-methylenebis(4-isocyanatocyclohexane), or mixtures thereof, preferably comprises or consists of diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 2,2'-diisocyanate, or mixtures thereof.

[0041] In a seventh embodiment, the invention relates to the process of any of the preceding embodiments, characterized in that the chain extender of component (C) is selected from the group comprising or consisting of ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 1,4-di(β-hydroxyethyl)hydroquinone, triethylene glycol, tetraethylene glycol or mixtures thereof, preferably selected from the group comprising or consisting of ethane-1,2-diol, butane-1,4-diol, hexane-1,6-diol, triethylene glycol or mixtures thereof.

[0042] In an eighth embodiment, the invention relates to the process of any of the preceding embodiments, characterized in that the additives, auxiliaries and / or additives of component (E) are selected from the group comprising or consisting of lubricants, in particular fatty acid esters, their metal soaps, fatty acid amides and silicon compounds; antiblocking agents; inhibitors; stabilizers; flame retardants; dyes; pigments; inorganic fillers; organic fillers; nucleating agents; reinforcing agents, in particular inorganic fibers; monofunctional chain terminators, in particular 1-butanol, 1-hexanol, 1-octanol, stearyl alcohol, 1-butylamine and stearylamine; or mixtures thereof.

[0043] In a ninth embodiment, the present invention relates to a process comprising the steps of: (i) reacting a mixture comprising all of component (A), a portion of component (B), and optionally some or all of component (D) and / or component (E) to form an NCO-functional prepolymer, wherein the molar ratio of component (B) (in part) to component (A) is in the range of 1.1:1.0 to 5.0:1.0; (ii) reacting the NCO-functional prepolymer from step (i) with the entire amount of component (C), optionally in the presence of a further portion or remainder of component (D) and / or component (E), to form an OH-functional prepolymer; (iii) reacting the OH-functional prepolymer from step (ii) with the remaining amount of component (B) and, if applicable, with the remaining amount of component (D) and / or component (E) to form a polyether-containing thermoplastic polyurethane; wherein in step (ii), preferably the molar ratio of NCO functional groups to OH functional groups in component (C) is less than 1.0.

[0044] In a tenth embodiment, the invention relates to the process of any of the preceding embodiments, wherein the reaction is carried out at an isocyanate index of 0.9 to 1.2, preferably 0.95 to 1.1, and more preferably 0.97 to 1.03.

[0045] In an eleventh embodiment, the present invention relates to a polyether-containing thermoplastic polyurethane obtained or obtainable by the process of any of the first to tenth embodiments.

[0046] In a twelfth embodiment, the present invention provides the polyether-containing thermoplastic polyurethane, a tensile strength, measured according to ISO 53504 (2009-10), of at least 17 MPa, preferably at least 22 to 60 MPa; and / or At least 30 KJ / m measured at -20°C according to DIN EN ISO179 / 1eA(2010) 2 , preferably 50 to 140 KJ / m 2 Charpy impact strength; 12. The polyether-containing thermoplastic polyurethane of claim 11, wherein

[0047] In a thirteenth embodiment, the present invention relates to the use of a polyether-containing thermoplastic polyurethane of embodiment 11 or 12 for producing injection-molded articles; extruded articles; pressed articles; compression-molded articles; 3D-printed articles; products for mechanical engineering, road construction and railway construction; medical and dental products, in particular aligners for treating crooked teeth; shoes, in particular ski boots; products for the automotive industry; products for the electrical industry, in particular cable sheaths, housings and plug connectors; consumer products; coatings; hoses; profiles; belts; films; fibers; nonwovens; textiles; damping elements; sealing elements.

[0048] In a fourteenth embodiment, the present invention relates to a product comprising the polyether-containing thermoplastic polyurethane of embodiment 11 or 12 or consisting of the polyether-containing thermoplastic polyurethane according to the invention, wherein the product is preferably a ski boot.

[0049] In a fifteenth embodiment, the present invention relates to the use of a C3 polyether homopolymer polyol in combination with a C2 polyether homopolymer polyol and / or a C2 / C3 polyether block copolymer polyol and / or a C4 polyether homopolymer polyol for increasing the low temperature impact strength and / or tensile strength of a polyether-containing thermoplastic polyurethane, in particular for increasing the low temperature impact strength and / or tensile strength of the polyether-containing thermoplastic polyurethane of embodiment 11 or 12, where the low temperature impact strength is measured in particular as Charpy impact strength. [Example]

[0050] Examples and Comparative Examples: The present invention will be described below with reference to examples, but the present invention is by no means limited to these examples.

[0051] Ingredients used: Polyol 1 = Polypropylene glycol (C3 polyether homopolymer polyol), starter propylene glycol (poly(propylene oxide) homopolymer); OH number approx. 56; proportion of secondary terminal OH groups: >90%; Polyol 2 = Terathane® 2000 (commercial product from Invista: polytetramethylene glycol; OH number approximately 56), (C4 polyether homopolymer polyol); Polyol 3 = Poly(propylene oxide)-poly(ethylene oxide) block copolymer (C2 / C3 polyether block copolymer polyol): alkylene oxide polymerized with propylene glycol (starter) (molar ratio of ethylene oxide units to propylene oxide units: approximately 51:49); OH number: approximately 56, proportion of primary terminal OH groups: >90%), KOH catalyst; Polyol 4 = polypropylene glycol (C3 polyether homopolymer polyol), starter propylene glycol (poly(propylene oxide) homopolymer), OH number approx. 28: proportion of secondary terminal OH groups: >90%); BDO = butane-1,4-diol (BDO, purity ≥ 99 wt%) was supplied by Ashland. TEG = triethylene glycol (TEG, purity ≥ 95 wt%) was supplied by Thermo Fischer (Kandel) GmbH. MDI = diphenylmethane 4,4'-diisocyanate (MDI, purity ≥ 99 wt%) was supplied by Covestro AG.

[0052] Measurement methods used: The OH number was titrated according to DIN 53240-2:2007-11; Tensile test: measured according to ISO 53504 (2009-10) at a pulling speed of 200 mm / min; Charpy impact strength test (low temperature impact strength): Charpy impact strength tests were carried out on injection-molded test specimens at -20°C in accordance with DIN EN ISO179 / 1eA (2010). The test specimens had the following dimensions: length 80±2 mm, width 10.0±0.2 mm, and thickness 4.0±0.2 mm. The test specimens were notched. The radius rN of the notch base was 0.25±0.05 mm.

[0053] Working Example: Table 1 illustrates the invention based on some examples, the preparation processes used are explained below.

[0054] Preparation (batch process): Step 1: Part 1 of MDI (see Table 1) is reacted with 1 mole of polyol or polyol mixture with stirring at about 140°C until conversion is greater than 90 mole % based on polyol.

[0055] Step 2: Add the chain extender to the stirred reaction mixture and stir vigorously for approximately 10 seconds.

[0056] Step 3: Add part 2 of MDI (see Table 1) to the stirred reaction mixture. The reaction mixture is stirred for an additional 20 seconds, then poured onto a metal sheet and heat treated at 120°C for 30 minutes.

[0057] The resulting TPU cast sheet was chopped and pelletized. The pellets were then heated at a temperature of 180°C to 230°C under a pressure of 650 to 750 bar for 10 to 35 cm. 3 The mixture was processed using an Arburg Allrounder 470S injection molding machine at an injection rate of 1 / s to give rods (mold temperature: 40°C; rod size: 80 × 10 × 4 mm) or plates (mold temperature: 70°C; size: 125 × 50 × 2 mm).

[0058] The mechanical properties (tensile strength and tensile elongation) and Charpy low temperature impact strength of the produced TPU products were measured.

[0059] Examples 1-18 describe batch processes.

[0060] Preparation (continuous process, e.g., reactive extruder): Similar to batch experiments, the TPU can also be compounded batchwise using, for example, a twin-screw reactive extruder (although the preparation is not necessarily limited to this format; see "Belt Process").

[0061] Using a gear pump, part 1 of MDI, preheated to 60°C, was metered into a tube equipped with a pin mixer. A second gear pump was used to inject the polyol or polyol mixture, heated to 140°C, into the same tube. The tube had a length / diameter ratio of 8:1. The reaction mixture flowed continuously into a connected twin-screw extruder, which was externally heated to 140°C to 220°C. At the middle of the screw, chain extender and part 2 of MDI were added. The screw shaft speed was 300 rpm. At the end of the screw, the hot melt was pelletized and cooled. The pellets were processed into test specimens by injection molding, and the properties listed in the table were measured.

[0062] Example 19 describes a continuous process (extruder process).

[0063] [Table 1]

[0064] *Comparative Example 1 and Comparative Example 18 are TPU formulations based on polypropylene glycol (C3 polyether homopolymer polyol), which TPUs cannot be manufactured or processed by injection molding.

[0065] *Comparative Example 3 and Comparative Examples 5-7 are formulations based on polypropylene-polyethylene glycol (C2 / C3 polyether block copolymer polyol), the TPUs of which can be produced with good tear strength but poor low temperature impact strength.

[0066] *Examples 4, 8-13, and 15-17 demonstrate TPU compounds containing a C2 / C3 polyether block copolymer polyol mixed with a C3 polyether homopolymer polyol that have good tear strength and good low temperature impact strength (Charpy impact strength).

[0067] *Comparative Example 14 shows a TPU formulation based on a mixture of C2 / C3 polyether block copolymer polyol mixed with polypropylene glycol (C3 polyether homopolymer polyol) in a ratio of about 80:20; this material exhibits good tear strength but unsatisfactory low temperature impact strength.

[0068] *Example 2 shows a TPU formulation based on a C3 ether polyol and a C4 polyether homopolymer polyol (also polyTHF or PTMEG) with good mechanical properties and good low temperature impact strength.

[0069] *Example 19 shows that the process of the present invention, involving a continuous process regime, also simultaneously provides good tear strength and good low temperature impact strength for the polyether-containing thermoplastic polyurethanes prepared.

Claims

1. A composition comprising or consisting of the following components: (A) at least one polyether homopolymer polyol; (B) at least one polyisocyanate; (C) at least one chain extender; (D) optionally, a catalyst; (E) optionally at least one additive, auxiliary and / or additive; 1. A process for preparing a polyether-containing thermoplastic polyurethane by reacting the polyether homopolymer polyol is a C3 polyether homopolymer polyol (A1), and component (A) further comprises at least one component (A2), wherein component (A2) comprises or consists of a C2 polyether homopolymer polyol and / or a C2 / C3 polyether block copolymer polyol and / or a C4 polyether homopolymer polyol, and wherein the weight ratio of component (A1) to component (A2) is from 95:5 to 25:75, based on the total weight of component (A1) and component (A2).

2. * The C2 polyether homopolymer polyol has a number average molecular weight in the range of 500 to 4000 g / mol, preferably in the range of 1000 to 3000 g / mol; * The C3 polyether homopolymer polyol has a number average molecular weight in the range of 500 to 8000 g / mol, preferably in the range of 1000 to 4500 g / mol; * The C2 / C3 polyether block copolymer polyol has a number average molecular weight in the range of 1000 to 4000 g / mol, preferably in the range of 1500 to 2500 g / mol; and / or * The C4 polyether homopolymer polyol has a number average molecular weight in the range of 500 to 4500 g / mol, preferably in the range of 1500 to 4500 g / mol; 2. The process according to claim 1 , characterized in that

3. 3. The process according to claim 1 or 2, characterized in that the theoretical hardness of the polyether-containing thermoplastic polyurethane is 40% or more; Here, the theoretical hardness is calculated by the following formula: Theoretical hardness = (n (chain extender) × M (polyisocyanate) + m (chain extender)) / m 総量 where: n = molar amount of component, M = molar mass of component, and m = mass of component.

4. 10. The process of any of the preceding claims, characterized in that the molar ratio of ethylene oxide units to propylene oxide units in the C2 / C3 polyether block copolymer polyol is from 95:5 to 5:95, preferably from 80:20 to 20:80, based on the molar amount of alkylene oxide used in preparing the polyether.

5. 10. The process according to any of the preceding claims, characterized in that the weight ratio of component (A1) to component (A2) is from 65:35 to 30:70, based on the total weight of component (A1) and component (A2).

6. 10. The process according to any of the preceding claims, characterized in that the polyisocyanate of component (B) comprises or consists of diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 2,2'-diisocyanate, hexamethylene 1,6-diisocyanate, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, isophorone diisocyanate, naphthylene 1,5-diisocyanate, 1,1'-methylenebis(4-isocyanatocyclohexane) or mixtures thereof, preferably comprising or consisting of diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 2,2'-diisocyanate or mixtures thereof.

7. 10. The process according to any of the preceding claims, characterized in that the chain extender of component (C) is selected from the group comprising or consisting of ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 1,4-di(β-hydroxyethyl)hydroquinone, triethylene glycol, tetraethylene glycol or mixtures thereof, preferably selected from the group comprising or consisting of ethane-1,2-diol, butane-1,4-diol, hexane-1,6-diol, triethylene glycol or mixtures thereof.

8. 10. The process according to any of the preceding claims, characterized in that the additives, auxiliaries and / or additives of component (E) are selected from the group comprising or consisting of lubricants, in particular fatty acid esters, their metal soaps, fatty acid amides and silicon compounds; antiblocking agents; inhibitors; stabilizers; flame retardants; dyes; pigments; inorganic fillers; organic fillers; nucleating agents; reinforcing agents, in particular inorganic fibers; monofunctional chain terminators, in particular 1-butanol, 1-hexanol, 1-octanol, stearyl alcohol, 1-butylamine and stearylamine; or mixtures thereof.

9. The process comprises the steps of: (i) reacting a mixture comprised of all of component (A), a portion of component (B), and optionally some or all of component (D) and / or component (E) to form an NCO-functional prepolymer, wherein the molar ratio of component (B) (in part) to component (A) is in the range of 1.1:1.0 to 5.0:1.0; (ii) reacting the NCO-functional prepolymer from step (i) with the entire amount of component (C), optionally in the presence of a further portion or remaining amount of component (D) and / or component (E), to produce an OH-functional prepolymer; (iii) reacting the OH-functional prepolymer from step (ii) with the remaining amount of component (B), and, if applicable, with the remaining amount of component (D) and / or component (E) to form a polyether-containing thermoplastic polyurethane; 10. The process according to claim 1, further comprising or consisting of the steps:

10. 10. The process according to any of the preceding claims, characterized in that the reaction is carried out at an isocyanate index of from 0.9 to 1.2, preferably from 0.95 to 1.1, more preferably from 0.97 to 1.

03.

11. A polyether-containing thermoplastic polyurethane obtained or obtainable by the process according to any of claims 1 to 10.

12. The polyether-containing thermoplastic polyurethane is a tensile strength, measured according to ISO 53504 (2009-10), of at least 17 MPa, preferably at least 22 to 60 MPa; and / or At least 30 KJ / m measured at -20°C according to DIN EN ISO 179 / 1eA (2010) ２ , preferably 50 to 140 KJ / m ２ Charpy impact strength; The polyether-containing thermoplastic polyurethane of claim 11, characterized in that it has

13. Use of polyether-containing thermoplastic polyurethanes according to claim 11 or 12 for the production of injection-molded articles; extrusion products; pressed products; compression-molded articles; 3D-printed products; products for mechanical engineering, road construction and railway construction; medical and dental products, in particular aligners for treating crooked teeth; shoes, in particular ski boots; products for the automotive industry; products for the electrical industry, in particular cable sheaths, housings and plug connectors; consumer products; coatings; hoses; profiles; belts; films; fibers; nonwoven fabrics; woven fabrics; damping elements; sealing elements.

14. 13. An article comprising or consisting of a polyether-containing thermoplastic polyurethane according to claim 11 or 12, wherein the article is preferably a ski boot.

15. 13. Use of a C3 polyether homopolymer polyol in combination with a C2 polyether homopolymer polyol and / or a C2 / C3 polyether block copolymer polyol and / or a C4 polyether homopolymer polyol for increasing the low-temperature impact strength and / or tensile strength of a polyether-containing thermoplastic polyurethane, in particular for increasing the low-temperature impact strength and / or tensile strength of a polyether-containing thermoplastic polyurethane according to claim 11 or 12, wherein the low-temperature impact strength is measured in particular as Charpy impact strength.

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