TPU containing cyclic additives

Abstract

The present invention relates to a composition comprising a thermoplastic polyurethane which is a reaction product of at least one diisocyanate (I1), at least one polyol (P1), and at least one chain extender (C1), and at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol as determined by GPC in accordance with DIN 55672-1 (2016-03-01) using DMF as a fluid agent and PMMA as a standard, wherein the polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. Furthermore, the present invention relates to a method for preparing a composition comprising the thermoplastic polyurethane and at least one component (CA1) according to the present invention, and to the use of the composition according to the present invention for the manufacture of molded bodies, coatings, hoses, films, nonwoven articles or fibers, foamed parts, particle foams, additive manufacturing filaments, 3D printing, and injection molded parts used in industrial applications, consumer goods including sports, automobiles, agriculture, and construction applications.

Description

Technical Field

[0001] The present invention relates to a thermoplastic polyurethane which is at least a reaction product of at least one diisocyanate (I1), at least one polyol (P1), and at least one chain extender (C1), and at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol (the molecular weight Mn is determined by GPC in accordance with DIN 55672-1 (2016-03-01) using a UV detector at a wavelength of 254 nm for distinguishing additives and using PMMA as a standard for detecting oligomers by using a refractive index (RI) detector for detecting oligomers with a molecular weight of less than 500 g / mol and detecting DMF as a flow agent), wherein the polyol (P1) contains a functional group (F1) selected from an ether group and an ester group in the polymer backbone, and the component (CA1) contains a functional group (F2) selected from an ether group and an ester group. Further, the present invention relates to a method for preparing a composition comprising the thermoplastic polyurethane according to the present invention and at least one component (CA1), and the use of the composition according to the present invention for the production of shaped bodies, coatings, hoses, films, non-woven articles or fibers, foamed parts, particle foams, additive manufacturing filaments, 3D printing, injection molded parts used in industrial applications, consumer goods including sports, automobiles, agriculture, and construction applications.

[0002] Methods for producing polyurethanes are already known based on the prior art. In the case of polyurethanes based on polyester polyols having a high molecular weight, blooming is frequently observed, which leads to undesirable material properties including the visual appearance of the material. It is very difficult to control this phenomenon. The prior art discloses various strategies for reducing the blooming phenomenon. The use of chain termination reagents or the use of specific polyester polyols based on propylene glycol for reducing the blooming phenomenon is widely described.

[0003] For example, International Publication No. 15 / 000722 discloses a polyurethane based on at least one polyisocyanate and at least one polyester polyol, wherein the polyester polyol is based on a mixture of at least one polyhydric alcohol and at least two dicarboxylic acids, and at least one of the at least two dicarboxylic acids is at least partially obtained from renewable raw materials, as well as a method for producing such polyurethane and a molded body containing such polyurethane. International Publication No. 2019 / 002263 discloses a thermoplastic polyurethane that can be obtained or obtained by reacting at least one polyisocyanate composition comprising at least one polyisocyanate, at least one chain extender and at least one polyol composition, wherein the polyol composition comprises at least one polyester polyol (P1) that can be obtained by reacting an aliphatic dicarboxylic acid having 2 to 12 carbon atoms with a mixture (M1) comprising propane-1,3-diol and a further diol (D1) having 2 to 12 carbon atoms, preferably butane-1,4-diol. The disclosed polyurethane exhibits a low blooming tendency.

[0004] European Patent Application Publication No. 0687695 relates to the controlled reduction of blooming phenomena by the addition of monofunctional alcohols to thermoplastic polyurethanes based on polyester polyols.

[0005] U.S. Patent No. 8,790,763 discloses the reduction of blooming by using a polyester polyol having 1,3-propylene glycol as a repeating unit.

[0006] International Publication No. 2012 / 173911 describes the production of thermoplastic polyurethanes with reduced blooming by using polyester polyols together with bio-based glycols.

[0007] U.S. Patent Application Publication No. 2003 / 0036621 relates to the reduction of blooming in thermoplastic polyurethanes by chain termination additives such as monofunctional alcohols (chain length > C14, monoisocyanates or monoamines).

[0008] International Publication No. 2009 / 103767 discloses the production of thermoplastic polyurethanes in which deposition formation is reduced by using various mixtures of alkanediols as chain extenders.

[0009] However, known methods based on prior art, while reducing the tendency to bloom, often result in polyurethanes that do not possess sufficiently good mechanical properties.

[0010] Therefore, the object of the present invention was to provide a thermoplastic polyurethane having good mechanical properties and a reduced tendency to bloom.

[0011] The objective is, according to the present invention, at least components (i) and (ii): (i) A thermoplastic polyurethane which is a reaction product of at least one diisocyanate (I1), at least one polyol (P1), and at least one chain extender (C1), and (ii) At least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, determined by GPC in accordance with DIN 55672-1 (2016-03-01), using a UV detector at a wavelength of 254 nm for differentiation from additives, and using a refractive index (RI) detector for the detection of oligomers, with DMF as a fluid agent and PMMA as a standard for the detection of oligomers less than 500 g / mol. A composition comprising, The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. This is achieved by the composition.

[0012] Surprisingly, the compositions according to the present invention were found to exhibit a significantly reduced tendency to bloom while maintaining good low-temperature flexibility and mechanical properties.

[0013] The composition according to the present invention comprises at least components (i) and (ii), and may comprise further components. The thermoplastic polyurethane present as component (i) is a reaction product of at least one diisocyanate (I1), at least one polyol (P1), and at least one chain extender (C1). The polyol (P1) used in the preparation contains a functional group (F1) selected from ether groups and ester groups according to the present invention in its polymer backbone. According to the present invention, the functional group in the polymer backbone may be a functional group that links monomer units. Preferably, at least a portion of the functional group (F1) is a functional group that links monomer units of the polyol (P1). In the context of the present invention, the polyol (P1) is preferably a polyether polyol or a polyester polyol. Component (CA1) has a molecular weight Mn in the range of 50 to 500 g / mol, determined by GPC in accordance with DIN 55672-1 (2016-03-01) using DMF as a fluid agent and PMMA as a standard, and contains a functional group (F2) selected from ether groups and ester groups. Preferably, component (CA1) is an oligomer, and the functional group (F2) links monomer units. More preferably, component (CA1) is an oligomer without reactive functional groups, particularly a cyclic oligomer. The polyol (P1) and component (CA1) may contain further functional groups. Preferably, the polyol (P1) and component (CA1) contain only functional groups selected from ether groups and ester groups.

[0014] In the context of the present invention, the functional groups (F1) and (F2) may be the same or different. Therefore, according to the present invention, the thermoplastic polyurethane may be based on a polyester polyol and component (CA1) may contain an ester group, or the thermoplastic polyurethane may be based on a polyester polyol and component (CA1) may contain an ether group, or the thermoplastic polyurethane may be based on a polyether polyol and component (CA1) may contain an ester group, or the thermoplastic polyurethane may be based on a polyether polyol and component (CA1) may contain an ether group.

[0015] In further embodiments, the present invention also relates to compositions disclosed above, wherein the functional groups (F1) and (F2) are the same as each other, for example, (F1) and (F2) are ether groups or (F1) and (F2) are ester groups.

[0016] In a further embodiment, the present invention also relates to the compositions disclosed above, wherein component (CA1) is polyester, preferably cyclic polyester.

[0017] A suitable polyester as component (CA1) is, for example, a reaction product of a dicarboxylic acid (a1) and a diol (d1). Suitable dicarboxylic acids and diols are, in principle, known and can be selected from, for example, the dicarboxylic acids and diols disclosed above. Preferably, the dicarboxylic acid (a1) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof. Suitable diols (d1) may be, for example, ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

[0018] In a further embodiment, the present invention also relates to the compositions disclosed above, wherein component (CA1) is a polyester which is a reaction product of a dicarboxylic acid (a1) and a diol (d1), the dicarboxylic acid (a1) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

[0019] It has also been found that mixtures of diols can be used. Accordingly, according to further embodiments, the present invention also relates to the compositions disclosed above in which a mixture of two diols selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol and hexanediol is used as diol (d1).

[0020] According to the present invention, a polyol (P1) is used in the preparation of a thermoplastic polyurethane. It is also possible to use a mixture of two or more polyols. Suitable polyols are, in principle, known to those skilled in the art.

[0021] Preferably, the polyol (P1) is a polyester polyol. Suitable polyester polyols are, in principle, known to those skilled in the art.

[0022] Preferably, according to the present invention, the polyol (P1) is selected from the group consisting of polyester polyols, and more preferably linear polyester polyols.

[0023] In a further embodiment, the present invention also relates to the compositions disclosed above, wherein the polyol (P1) is a polyester polyol.

[0024] Suitable polyester polyols, particularly polyester diols, can be prepared, for example, from a dicarboxylic acid having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and a polyhydric alcohol. Examples of useful dicarboxylic acids include aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, and sebacic acid, or aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, and terephthalic acid. Dicarboxylic acids can be used individually or in the form of mixtures, for example, a mixture of succinic acid, sebacic acid, and adipic acid. For the preparation of polyester diols, it may be more advantageous to use a corresponding dicarboxylic acid derivative instead of a dicarboxylic acid, such as a carboxylic acid diester having 1 to 4 carbon atoms in the alcohol radical, such as dimethyl terephthalate or dimethyl adipic acid, a carboxylic acid anhydride, such as succinic anhydride, glutaric anhydride, or phthalic anhydride, or carbonyl chloride. Examples of polyhydric alcohols include glycols having 2 to 10, preferably 2 to 6, carbon atoms, such as ethylene glycol, diethylene glycol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol, 2,2-dimethylpropane-1,3-diol, propane-1,3-diol, 2-methylpropane-1,3-diol, 3-methylpentane-1,5-diol, or dipropylene glycol. Polyhydric alcohols can be used individually or in mixtures, for example, in the form of a mixture of butane-1,4-diol and / or propane-1,3-diol. In addition, low molecular weight, highly functional polyols, such as 1,1,1-trimethylolpropane or pentaerythritol, may be included in small amounts up to 3% by weight of the total reaction mixture. According to the present invention, it is preferable to use only bifunctional starting compounds.

[0025] The molecular weight of the polyol (P1) used can take on a wide range of values. Preferred examples include polyols having an average molecular weight in the range of 500 to 3500 g / mol, and more preferably in the range of 800 to 3000 g / mol.

[0026] The molecular weight of the polyester polyol used can also take values within a wide range. Preferred examples include polyester polyols having an average molecular weight in the range of 2000 to 3500 g / mol, more preferably in the range of 2500 to 3200 g / mol.

[0027] Generally, the polyester polyol (P1) used is a reaction product of a dicarboxylic acid (a2) and a diol (d2). When a mixture of dicarboxylic acids is used, the ratio is generally in the range of 9:1 to 1:9, preferably in the range of 8:2 to 2:8.

[0028] Preferably, the dicarboxylic acid (a2) is selected from the group consisting of adipic acid, succinic acid or a mixture thereof. Preferably, the diol (d2) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol and hexanediol, or a mixture thereof.

[0029] According to a further embodiment, the present invention relates to a polyester polyol in which the polyol is a reaction product of a dicarboxylic acid (a2) and a diol (d2), the dicarboxylic acid (a2) is selected from the group consisting of adipic acid, succinic acid or a mixture thereof, and the diol (d2) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol and hexanediol, or a mixture thereof, and also relates to the composition disclosed above.

[0030] In the context of the present invention, it is particularly preferred that the diol (d1) and the diol (d2) are the same as each other. Also, the dicarboxylic acid (a1) and the dicarboxylic acid (a2) may be the same as each other in the context of the present invention.

[0031] According to the present invention, the polyol (P1) may be a polyether polyol, such as a polyether polyol such as polytetramethylene ether glycol, polyethylene glycol or polypropylene glycol.

[0032] In a further embodiment, the present invention also relates to the compositions disclosed above, wherein the polyol (P1) is a polyether polyol. In a further embodiment, the present invention also relates to the compositions disclosed above, wherein the polyol is a polyether polyol selected from the group consisting of polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol.

[0033] The molecular weight of the polyether polyol used can also take on a wide range of values. Suitable examples include polyether polyols having an average molecular weight in the range of 600 to 3000 g / mol, preferably in the range of 800 to 2000 g / mol, and more preferably in the range of 1000 to 1800 g / mol.

[0034] When the polyol (P1) is a polyether polyol, component (CA1) may be a polyester or a polyether. Preferably, when the polyol (P1) is a polyether polyol, component (CA1) preferably also includes an ether group. Component (CA1) may be, for example, a cyclic polyether, for example, a crown ether. Suitable components are, in principle, known to those skilled in the art and may be, for example, oligomers of ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, or 1,4-butylene oxide.

[0035] In a further embodiment, the present invention also relates to the compositions disclosed above, wherein component (CA1) is a polyether, preferably a cyclic polyether.

[0036] In further embodiments, the present invention also relates to the compositions disclosed above, wherein component (CA1) is a cyclic oligomer of ethylene oxide, 2-propylene oxide, 1,3-propylene oxide, or 1,4-butylene oxide.

[0037] According to the present invention, it is also possible to use a mixture of two or more polyols in the preparation of thermoplastic polyurethane. The polyol or polyol composition used preferably has an average functional value in the range of 1.7 to 2.3, preferably in the range of 1.9 to 2.1, and particularly 2.

[0038] Suitable polyols are described, for example, in “Kunststoffhandbuch [Plastics Handbook], volume 7, Polyurethane [Polyurethanes]”, Carl Hanser Verlag, 3rd edition 1993, chapter 3.1.

[0039] According to the present invention, the polyol composition may contain a solvent. Suitable solvents are known to those skilled in the art.

[0040] According to the present invention, a chain extender (C1) is used in the preparation of a thermoplastic polyurethane. Suitable chain extenders are known to those skilled in the art.

[0041] The chain extender used is a compound having at least two groups reactive with isocyanates. These reactive groups may be NH, OH, or SH groups. Suitable examples include diamines, diols, or water. It is preferable to use at least one chain extender selected from the group consisting of compounds having at least two isocyanate-reactive groups and a molecular weight of less than 500 g / mol.

[0042] Therefore, in further embodiments, the present invention also relates to a method for producing the above polyurethane, wherein the chain extender (C1) is selected from the group consisting of diols, diamines, and / or water.

[0043] The chain extenders used may be, for example, well-known aliphatic, araliphatic, aromatic and / or alicyclic compounds having a molecular weight of 50 to 499 g / mol, preferably bifunctional compounds, such as alkanediols having 2 to 10 carbon atoms in the alkylene radical, for example, diols selected from the group consisting of C2 to C6 diols, preferably butane-1,4-diol, hexane-1,6-diol, and / or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols having 3 to 8 carbon atoms, preferably unbranched alkanediols, particularly propane-1,3-diol, butane-1,4-diol and hexane-1,6-diol.

[0044] Here, more preferably, aliphatic, aromaticaliphatic, aromatic and / or alicyclic diols having a molecular weight of 50 g / mol to 220 g / mol can be used. Alkanediols having 2 to 12 carbon atoms in the alkylene radical, particularly di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols, are preferred. In the present invention, ethanediols, propanediols, butanediols, pentanediols, hexanediols, or mixtures thereof are particularly preferred.

[0045] According to the present invention, it is also possible to use a mixture of two or more chain extenders.

[0046] In the context of the present invention, the amounts used for the chain extender and the polyol composition can take on a wide range of values. For example, in the context of the present invention, the chain extender (C1) can be used in an amount ranging from 1:40 to 10:1, depending on the polyol (P1) used.

[0047] In a further embodiment, the present invention also relates to the compositions disclosed above, wherein the chain extender (C1) is selected from the group consisting of ethanediols, propanediols, butanediols, pentanediols, hexanediols, or mixtures thereof.

[0048] According to the present invention, diisocyanate (I1) is used in the preparation of thermoplastic polyurethanes. Preferred diisocyanates in the context of the present invention are aliphatic or aromatic diisocyanates, particularly aromatic diisocyanates.

[0049] In addition, in the context of the present invention, a pre-reacted product may be used as the isocyanate component, in which case the polyol is reacted with the isocyanate in a preceding reaction step. The resulting product essentially has isocyanate terminal groups and can be used in accordance with the present invention.

[0050] The aliphatic diisocyanates used are typically aliphatic and / or alicyclic diisocyanates, such as tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanates, 2-methylpentamethylene 1,5-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, trimethylhexamethylene 1,6-diisocyanate, and 1,3-bis(I) These are socyanate-methyl)cyclohexane (H6XDI), 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, and methylenedicyclohexyl 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI).

[0051] Preferred aliphatic polyisocyanates include hexamethylene 1,6-diisocyanate (HDI), pentamethylene 1,5-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, and methylenedicyclohexyl 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI).

[0052] Preferred aromatic diisocyanates include, in particular, naphthylene 1,5-diisocyanate (NDI), torylene 2,4- and / or 2,6-diisocyanate (TDI), diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), xylylene diisocyanate (XDI), p-phenylene diisocyanate (PDI), diphenylethane 4,4'-diisocyanate (EDI), diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl diisocyanate, diphenylethane 1,2-diisocyanate, and / or phenylene diisocyanate.

[0053] In the context of the present invention, it is also possible to use highly functional isocyanates, such as triisocyanates, e.g., triphenylmethane 4,4',4''-triisocyanate, as well as cyanurates of the diisocyanates described above, and oligomers obtained by partial reactions of diisocyanates with water, e.g., biuretes of the diisocyanates described above, as well as oligomers obtained by controlled reactions of semiblocked diisocyanates with polyols having an average of more than two, preferably three or more hydroxyl groups.

[0054] For example, polyisocyanate (I1) may be selected from the group consisting of diphenylmethane 2,2'-, 2,4'- and 4,4'-diisocyanates (MDI), torylene 2,4- and 2,6-diisocyanates (TDI), hexamethylene diisocyanate (HDI), 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI), or naphthalene 1,5-diisocyanate (NDI).

[0055] Accordingly, in further embodiments, the present invention also relates to a method for producing the above polyurethane, wherein the polyisocyanate (I1) is selected from the group consisting of diphenylmethane 2,2'-, 2,4'- and 4,4'-diisocyanate (MDI), torylene 2,4- and 2,6-diisocyanate (TDI), hexamethylene diisocyanate (HDI), 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI), or naphthalene 1,5-diisocyanate (NDI). The polyisocyanate (I2) is preferably selected from the group consisting of diphenylmethane 2,2'-, 2,4'- and 4,4'-diisocyanates (MDI), torylene 2,4- and 2,6-diisocyanates (TDI), hexamethylene diisocyanate (HDI), 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI), and naphthalene 1,5-diisocyanate (NDI).

[0056] In further embodiments, the present invention also relates to compositions disclosed above, wherein the isocyanate is selected from the group consisting of diphenylmethane 2,2'-, 2,4'- and 4,4'-diisocyanate (MDI), hexamethylene diisocyanate (HDI), p-phenylene diisocyanate (PDI), 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI), naphthalene 1,5-diisocyanate (NDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), and mixtures thereof.

[0057] When a mixture of two isocyanates is used, the isocyanates are typically used in a ratio of 1:20 to 1:3.

[0058] It has been found that the presence of component (CA1) mixed with the thermoplastic polyurethane according to the present invention results in improved properties of the composition. The amount of component (CA1) in the composition may vary depending on the thermoplastic polyurethane and component (CA1) used. Typically, the amount of the migratory portion in the composition is in the range of 70 to 300 ppm by weight, particularly in the range of 50 to 500 ppm, relative to the total composition.

[0059] The amount of the migratory portion is determined by GPC in accordance with DIN 55672-1 (2016-03-01), using DMF as a fluid agent and PMMA as a standard for detecting oligomers less than 500 g / mol. Distinction from additives is achieved by using a UV detector at a wavelength of 254 nm, and oligomer detection is achieved by using a refractive index (RI) detector.

[0060] In a further embodiment, the present invention also relates to the compositions disclosed above, wherein the proportion of component (CA1) in the composition based on the migratory portion is in the range of 50 to 500 ppm by weight relative to the whole composition.

[0061] The amount of component (CA1) determined using GPC may be higher, for example, up to 4% of the total composition.

[0062] The proportion of thermoplastic polyurethane in the composition may vary, but is typically in the range of 75% to 99.9% by weight of the total composition, preferably in the range of 80% to 99.9% by weight of the total composition.

[0063] In a further embodiment, the present invention also relates to the compositions disclosed above, wherein the proportion of thermoplastic polyurethane in the composition is in the range of 75% to 99.9% by weight relative to the whole composition.

[0064] The molecular weight of thermoplastic polyurethane can take on a wide range of values. It is particularly advantageous for thermoplastic polyurethane to have a molecular weight in the range of 20,000 to 500,000 g / mol, more preferably 50,000 to 300,000 g / mol, especially 80,000 to 250,000 g / mol, and preferably 90,000 to 200,000 g / mol, as determined using GPC.

[0065] According to the present invention, further additives may be added to the composition. Additives and auxiliaries are known to those skilled in the art. According to the present invention, it is also possible to use a combination of two or more additives.

[0066] In the context of the present invention, the term “additive” is understood more specifically to mean catalysts, auxiliaries and additives, particularly stabilizers, nucleating agents, release agents, mold release aids, fillers, flame retardants or crosslinking agents.

[0067] Suitable additives include, for example, stabilizers, nucleating agents, fillers, and silicates.

[0068] Examples of auxiliary agents and additives include surfactants, flame retardants, nucleating agents, oxidation stabilizers, antioxidants, lubricants and mold release agents, dyes and pigments, stabilizers against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents, and plasticizers. Suitable auxiliary agents and additives can be found, for example, in Kunststoffhandbuch, volume VII, edited by Vieweg and Hoechtlen, Carl Hanser Verlag, Munich 1966 (pp. 103-113).

[0069] In a further embodiment, the present invention also relates to a method for preparing a composition comprising a thermoplastic polyurethane and at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol. In the context of the present invention, for example, component (CA1) and the thermoplastic polyurethane can be mixed in a suitable apparatus. Component (CA1) can also be added to one or more components used in the preparation of the thermoplastic polyurethane. For example, component (CA1) can be added in a suitable amount to a polyol (P1) or a chain extender used.

[0070] When component (CA1) is added to a polyol or chain extender, the amount of component (CA1) is adjusted so that a suitable amount of component (CA1) is obtained in the resulting thermoplastic polyurethane. The suitable amount may be in the range of 10 to 2000 ppm, for example, based on the weight of the polyol component.

[0071] According to the present invention, it is also possible to use a suitable polyol that may contain component (CA1) as a result of its preparation process. If the polyol contains component (CA1) as a result of its preparation process, the amount of component (CA1) can be adjusted, for example, by using a suitable purification step. According to the present invention, it is also possible to adjust the amount of component (CA1) in the polyol by adjusting the conditions of the polyol preparation process, such as temperature, pressure, or the catalyst and reaction time used, in order to obtain a polyol containing a suitable amount of component (CA1). The polyol may contain further components with a molecular weight of less than 500 g / mol, such as reactive oligomers that can react with isocyanate groups. Preferably, the amount of components with a molecular weight of less than 500 g / mol that do not have functional groups that can react with isocyanate groups is adjusted to a range of 30 to 2000 ppm or 50 to 1000 ppm based on the weight of the polyol components. This amount can also be adjusted depending on the polyol and isocyanate used.

[0072] The amount of low molecular weight by-products in polyols is preferably determined by GPC in accordance with DIN 55672-1 (2016-03-01), using THF as a fluidizing agent and PEG as a standard for detecting oligomers less than 500 g / mol. Distinction from additives is usually performed by a UV detector at a wavelength of 254 nm, and oligomer detection is usually performed by a refractive index (RI) detector. In addition, the proportion of oligomers less than 500 g / mol can be determined by thermal desorption GC-MS in accordance with VDA 278 (FOG run only). To determine the amount of migratory portion, the proportion of oligomers less than 500 g / mol was determined by weighing 2-4 mg at 120°C for 10 minutes using thermal desorption GC-MS in accordance with VDA 278 (FOG run only). Evaluation was performed using total ion chromatography (TIC). The obtained values ​​are calculated as hexadecane equivalents (ppmHdE).

[0073] GPC is typically used to determine the low molecular weight fraction in thermoplastic polyurethanes. According to the present invention, the proportion of low molecular weight compounds can be quantitatively analyzed by GPC at a flow rate of 1.50 mL / min using dimethylformamide (DMF) as the eluent. A PSS SDV linear XL 5 μm column is used, toluene is used as the standard, and the solution is calibrated against a congener of polymethyl methacrylate. The content (total low molecular weight content) determined by this method is typically up to 3.5% of the total composition.

[0074] Furthermore, the content of the migratory portion can be determined. To determine the content of the migratory portion, the injection-molded plate is typically first stored at 100°C for 20 hours, and then the content of the oligomer with a molecular weight of 500 g / mol is determined by thermal desorption GC-MS similar to VDA 278 (FOG run only) with a desorption time of 60 minutes. Evaluation was performed using total ion chromatography (TIC). The obtained values ​​are calculated as hexadecane equivalents (ppmHdE) (Method 2). Each content is given as the total content of the migratory portion in the context of the present invention. In the case of monocyclic (e.g., consisting of ADS and 1,4-butanediol) or ethers, the proportion of the crown ether, particularly the crown ether consisting of three THF molecules, was determined by peak size (Method 3). Each content is given as the content of the cyclic migratory portion in the context of the present invention.

[0075] Preferably, the total content of the migratory moiety of the compound having a molecular weight Mn in the range of 50 to 500 g / mol in the thermoplastic polyurethane is greater than 130 ppmHde, and more particularly in the range of 130 to 400 ppmHde. The content of the cyclic migratory moiety is typically in the range of 55 to 280 ppmHde, and more particularly in the range of 60 to 270 ppmHde, relative to the whole composition.

[0076] Therefore, according to further embodiments, the present invention also relates to the compositions disclosed above, wherein the proportion of component (CA1) given as the content of the cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition.

[0077] In a further embodiment, the present invention relates to a method for preparing a composition comprising a thermoplastic polyurethane and at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, determined by GPC in accordance with DIN 55672-1 (2016-03-01), using a UV detector at a wavelength of 254 nm to distinguish it from additives, and using a refractive index (RI) detector to detect oligomers, with DMF as a fluid agent and PMMA as a standard for detecting oligomers less than 500 g / mol, Thermoplastic polyurethane comprising at least components (a), (b), and (c): (a) at least one diisocyanate (I1), (b) at least one polyol composition (PC1), and (c) at least one chain extender (C1) Prepared by reacting, The polyol composition comprises at least one polyol (P1) and at least one component (CA1), The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. It also concerns the method.

[0078] Further additives, optional auxiliaries, or catalysts may be used as component (d) for the preparation of thermoplastic polyurethane.

[0079] According to the present invention, a polyol composition (PC1) containing a polyol (P1) is reacted with a diisocyanate (I1). The polyol composition (PC1) contains at least one polyol (P1) and may contain further polyols or further components, such as a solvent. According to the present invention, the diisocyanate (I1) may contain further components, such as a solvent.

[0080] The reaction can be carried out in apparatus known to those skilled in the art, such as a heated / cooled agitated tank or reaction extruder. The reaction is typically carried out at temperatures known to those skilled in the art, such as in the range of 20 to 250°C, preferably in the range of 40 to 130°C, and more preferably in the range of 70 to 90°C.

[0081] According to the present invention, the method may also include further steps, such as pretreatment of components or posttreatment of the obtained thermoplastic polyurethane, such as heat treatment. Therefore, in further embodiments, the present invention also relates to a method for producing the above-mentioned thermoplastic polyurethane, wherein the obtained thermoplastic polyurethane is heat-treated after the reaction.

[0082] Therefore, the present invention also relates to polyurethanes that can be obtained or obtained by the method of the present invention.

[0083] For preferred embodiments, refer to the above description of the method of the present invention. Therefore, in further embodiments, the present invention also relates to the above polyurethane, wherein the polyurethane is thermoplastic.

[0084] The polyurethanes of the present invention, and the polyurethanes obtained or obtainable by the methods of the present invention, can be further processed by processes known to those skilled in the art, such as injection molding, calendering, or extrusion, to obtain desired films, molded articles, rolls, fibers, automotive trims, hoses, cable connectors, bellows, hanging cables, cable sheaths, gaskets, belts, or damping elements.

[0085] Polyurethanes produced according to the present invention can be advantageously used in all applications specific to thermoplastic polyurethanes. Accordingly, the present invention also relates to thermoplastic polyurethanes that can be obtained by the above method for the manufacture of molded bodies, adhesives, coatings, hoses, films, nonwoven articles or fibers, or to the use of the above polyurethanes.

[0086] In a further embodiment, the present invention also relates to the use of compositions disclosed above or compositions prepared according to the methods disclosed above for the manufacture of molded bodies, coatings, tubes, rolls, belts, damping elements, cable sheaths, hoses, films, nonwoven articles or fibers, foamed parts, particle foams, additive manufacturing filaments, 3D printing, extruded parts, injection molded parts, agricultural and construction applications.

[0087] The expandable thermoplastic polyurethane beads according to the present invention belong to the group of particle foams, also known as foamed pellets (or bead foams, particle foams, expandable thermoplastic elastomer particles, or expandable thermoplastic polyurethane beads). Particle foams based on thermoplastic polyurethane or other thermoplastic elastomers and molded articles (also known as molded articles) made therefrom are, in principle, publicly known (e.g., International Publication No. 94 / 20568, International Publication No. 2007 / 082838, International Publication No. 2017 / 030835, International Publication No. 2013 / 153190, International Publication No. 2010 / 010010) and can be used in many ways.

[0088] In the sense of the present invention, foamed pellets, or more specifically, particle foam or bead foam, refer to a form of particles, where the average length of the particles is preferably in the range of 1 to 10 mm. In the case of non-spherical, for example, elliptical particles, the average length refers to the longest dimension in terms of length (determined, for example, by 3D evaluation of the granules by dynamic image analysis using an optical measuring device named "PartAn 3D" from Microtrac).

[0089] The single-form granules according to the present invention preferably have an average mass in the range of 0.1 to 50 mg, more preferably in the range of 0.5 to 45 mg. In this context, the average mass means the arithmetic mean based on the sample size of 10 different particles, each particle being weighted three times.

[0090] The foamed pellets according to the present invention typically have a bulk density of 30 g / l to 250 g / l, preferably 50 g / l to 200 g / l, and more preferably 70 g / l to 180 g / l. The bulk density is measured in accordance with DIN ISO 60:1999, and in determining the above values, a 10-l container is used instead of a 0.1-l container, as opposed to the standard. This is because measurements in a volume of only 0.1-l are too inaccurate, especially for low-density and high-mass foam particles.

[0091] Methods for producing foamed pellets and molded articles containing foamed pellets are, in principle, known to those skilled in the art and are disclosed, for example, in International Publication No. 2013 / 153190.

[0092] The shape of the pellets used in accordance with the present invention can vary. Not only circular, non-spherical, elongated or cylindrical particles, but also pellets having, for example, flat surfaces can be used.

[0093] The shape and dimensions of the foam pellets in the molded body may differ from those of the foam pellets used in the method, depending on the method conditions. For example, even if circular foam pellets are used in the method, the foam pellets in the molded body may have circular or non-spherical shapes, and can be, for example, elongated or cylindrical pellets, as well as pellets with flat surfaces. The average length of the foam pellets in the molded body may be, for example, in the range of 1 to 15 mm, preferably 1 to 8 mm. In the case of non-spherical shapes, elongated or cylindrical particles refer to the longest dimension in terms of length.

[0094] The melting of the foam pellets is preferably carried out in a mold to form the resulting molded body. In principle, all suitable methods for melting the foam pellets, such as melting at elevated temperatures, e.g., steam chest molding; molding at high frequencies, e.g., molding using electromagnetic radiation; a process using a double belt press; or a variotherm process, can be used in accordance with the present invention.

[0095] Further embodiments of the present invention are evident from the claims and examples. It will be understood that the features of the product / method / use according to the present invention, mentioned above and described below, can be used not only in the combinations specified in each case, but also in other combinations that do not depart from the scope of the invention. For example, combinations of preferred features and particularly preferred features, or combinations of uncharacterized features and particularly preferred features, are implicitly included even if these combinations are not explicitly mentioned.

[0096] The present invention is described in more detail by the following embodiments and combinations of embodiments, which are evident from the corresponding dependent references and other references. In particular, it should be noted that in any instance where the scope of an embodiment is referred to, for example, in the context of expressions such as "the method according to any one of Embodiments 1 to 4," each embodiment within that scope is deemed to be expressly disclosed to those skilled in the art, that is, the wording of this expression should be understood to those skilled in the art as synonymous with "the method according to any one of Embodiments 1, 2, 3, and 4."

[0097] 1. At least components (i) and (ii): (i) A thermoplastic polyurethane which is a reaction product of at least one diisocyanate (I1), at least one polyol (P1), and at least one chain extender (C1), and (ii) Using DMF as a fluid agent and PMMA as a standard, at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, as determined by GPC in accordance with DIN 55672-1 (2016-03-01). A composition comprising, The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. composition.

[0098] 2. The composition according to Embodiment 1, wherein the functional groups (F1) and (F2) are the same as each other.

[0099] 3. The composition according to Embodiment 1 or 2, wherein the polyol (P1) is a polyester polyol.

[0100] 4. A composition according to any one of Embodiments 1 to 3, wherein component (CA1) is polyester, preferably a cyclic polyester.

[0101] 5. The composition according to any one of Embodiments 1 to 4, wherein component (CA1) is a polyester which is a reaction product of a dicarboxylic acid (a1) and a diol (d1), the dicarboxylic acid (a1) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

[0102] 6. The composition according to Embodiment 5, wherein a mixture of two diols selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol is used as diol (d1).

[0103] 7. The composition according to any one of Embodiments 1 to 6, wherein the polyol is a polyester polyol which is a reaction product of a dicarboxylic acid (a2) and a diol (d2), the dicarboxylic acid (a2) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d2) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

[0104] 8. The composition according to Embodiment 1 or 2, wherein the polyol (P1) is a polyether polyol.

[0105] 9. The composition according to any one of Embodiments 1 to 8, wherein component (CA1) is a polyether, preferably a cyclic polyether.

[0106] 10. A composition according to any one of Embodiments 1 to 9, wherein component (CA1) is a cyclic oligomer of ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, or 1,4-butylene oxide.

[0107] 11. The composition according to any one of Embodiments 1 to 10, wherein the polyol (P1) is a polyether polyol selected from the group consisting of polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol.

[0108] 12. The composition according to any one of Embodiments 1 to 11, wherein the chain extender (C1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, hexanediol, or mixtures thereof.

[0109] 13. The composition according to any one of Embodiments 1 to 12, wherein the isocyanate is selected from the group consisting of methylenediphenyl diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI), p-phenylenediisocyanate (PDI), 2,2'-diisocyanate (H12MDI), naphthylene 1,5-diisocyanate (NDI), isophorone diisocyanate (IPDI), and mixtures thereof.

[0110] 14. The composition according to any one of Embodiments 1 to 13, wherein the proportion of component (CA1) given as the content of the cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition.

[0111] 15. A composition according to any one of Embodiments 1 to 13, wherein the proportion of a component (CA1) given as the content of a cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition, the content of the migratory portion is determined using an injection molding plate, which is first stored at 100°C for 20 hours, and then the content of an oligomer with a molecular weight of 500 g / mol is determined by thermal desorption GC-MS similar to VDA 278 (FOG run only) with a desorption time of 60 minutes, the evaluation is performed using a total ion chromatogram (TIC), the content is calculated as hexadecane equivalent (ppmHdE), and the proportion of oligomers is determined by the peak size.

[0112] 16. The composition according to any one of Embodiments 1 to 15, wherein the proportion of thermoplastic polyurethane in the composition is in the range of 75% to 99.9% by weight relative to the whole composition.

[0113] 17. A method for preparing a composition comprising thermoplastic polyurethane and at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, determined by GPC in accordance with DIN 55672-1 (2016-03-01), using DMF as a fluid agent and PMMA as a standard, Thermoplastic polyurethane comprising at least components (a), (b), and (c): (a) at least one diisocyanate (I1), (b) at least one polyol composition (PC1), and (c) at least one chain extender (C1) Prepared by reacting, The polyol composition comprises at least one polyol (P1) and at least one component (CA1), The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. method.

[0114] 18. The method according to Embodiment 17, wherein the functional groups (F1) and (F2) are the same as each other.

[0115] 19. The method according to Embodiment 17 or 18, wherein the polyol (P1) is a polyester polyol.

[0116] 20. The method according to any one of Embodiments 17 to 19, wherein component (CA1) is polyester, preferably cyclic polyester.

[0117] 21. The method according to any one of Embodiments 17 to 20, wherein component (CA1) is a polyester which is a reaction product of a dicarboxylic acid (a1) and a diol (d1), the dicarboxylic acid (a1) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

[0118] 22. The method according to Embodiment 21, wherein a mixture of two diols selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol is used as the diol (d1).

[0119] 23. The method according to any one of Embodiments 17 to 22, wherein the polyol is a polyester polyol which is a reaction product of a dicarboxylic acid (a2) and a diol (d2), and the dicarboxylic acid (a2) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d2) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

[0120] 24. The method according to Embodiment 17 or 18, wherein the polyol (P1) is a polyether polyol.

[0121] 25. The method according to any one of Embodiments 17 to 24, wherein component (CA1) is a polyether, preferably a cyclic polyether.

[0122] 26. The method according to any one of Embodiments 17 to 25, wherein component (CA1) is a cyclic oligomer of ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, or 1,4-butylene oxide.

[0123] 27. The method according to any one of Embodiments 17 to 26, wherein the polyol (P1) is a polyether polyol selected from the group consisting of polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol.

[0124] 28. The method according to any one of Embodiments 17 to 27, wherein the chain extender (C1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, hexanediol, or mixtures thereof.

[0125] 29. The method according to any one of Embodiments 17 to 28, wherein the isocyanate is selected from the group consisting of methylenediphenyl diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI), p-phenylenediisocyanate (PDI), 2,2'-diisocyanate (H12MDI), naphthylene 1,5-diisocyanate (NDI), isophorone diisocyanate (IPDI), and mixtures thereof.

[0126] 30. The method according to any one of Embodiments 17 to 29, wherein the proportion of component (CA1) given as the content of the cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition.

[0127] 31. The method according to any one of Embodiments 17 to 29, wherein the proportion of a given component (CA1) as the content of the cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition, the content of the migratory portion is determined using an injection molding plate, which is first stored at 100°C for 20 hours, and then the content of an oligomer with a molecular weight of 500 g / mol is determined by thermal desorption GC-MS similar to VDA 278 (FOG run only) with a desorption time of 60 minutes, the evaluation is performed using a total ion chromatogram (TIC), the content is calculated as hexadecane equivalent (ppmHdE), and the proportion of oligomers is determined by the peak size.

[0128] 32. The method according to any one of Embodiments 17 to 31, wherein the proportion of thermoplastic polyurethane in the composition is in the range of 75% to 99.9% by weight relative to the whole composition.

[0129] 33. Use of compositions prepared according to any one of Embodiments 1 to 16 or methods described in any one of Embodiments 17 to 32 for the manufacture of molded bodies, coatings, tubes, rolls, belts, damping elements, cable sheaths, hoses, films, nonwoven articles or fibers, foamed parts, particle foams, additive manufacturing filaments, 3D printing, extruded parts, and injection molded parts used in industrial applications, consumer goods including sports, automotive, agricultural, and construction applications.

[0130] 34. At least components (i) and (ii): (i) A thermoplastic polyurethane which is a reaction product of at least one diisocyanate (I1), at least one polyol (P1), and at least one chain extender (C1), and (ii) Using DMF as a fluid agent and PMMA as a standard, at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, as determined by GPC in accordance with DIN 55672-1 (2016-03-01). A composition comprising, The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. The polyol (P1) is a polyester polyol, and the component (CA1) is a polyester, preferably a cyclic polyester. composition.

[0131] 35. The composition according to Embodiment 34, wherein the functional groups (F1) and (F2) are the same as each other.

[0132] 36. The composition according to Embodiment 34 or 35, wherein component (CA1) is a polyester which is a reaction product of a dicarboxylic acid (a1) and a diol (d1), the dicarboxylic acid (a1) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

[0133] 37. The composition according to Embodiment 36, wherein a mixture of two diols selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol is used as diol (d1).

[0134] 38. The composition according to any one of Embodiments 34 to 37, wherein the polyol is a polyester polyol which is a reaction product of a dicarboxylic acid (a2) and a diol (d2), the dicarboxylic acid (a2) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d2) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

[0135] 39. The composition according to any one of embodiments 34 to 38, wherein the chain extender (C1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, hexanediol, or mixtures thereof.

[0136] 40. The composition according to any one of embodiments 34 to 39, wherein the isocyanate is selected from the group consisting of methylenediphenyl diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI), p-phenylenediisocyanate (PDI), 2,2'-diisocyanate (H12MDI), naphthylene 1,5-diisocyanate (NDI), isophorone diisocyanate (IPDI), and mixtures thereof.

[0137] 41. The composition according to any one of embodiments 34 to 40, wherein the proportion of component (CA1) given as the content of the cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition.

[0138] 42. A composition according to any one of Embodiments 34 to 40, wherein the proportion of a component (CA1) given as the content of a cyclic migratory moiety in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition, the content of the migratory moiety is determined using an injection molding plate, which is first stored at 100°C for 20 hours, and then the content of an oligomer with a molecular weight of 500 g / mol is determined by thermal desorption GC-MS similar to VDA 278 (FOG run only) with a desorption time of 60 minutes, the evaluation is performed using a total ion chromatogram (TIC), the content is calculated as hexadecane equivalent (ppmHdE), and the proportion of oligomers is determined by the peak size.

[0139] 43. The composition according to any one of Embodiments 34 to 42, wherein the proportion of thermoplastic polyurethane in the composition is in the range of 75% to 99.9% by weight relative to the whole composition.

[0140] 44. A method for preparing a composition comprising thermoplastic polyurethane and at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, determined by GPC in accordance with DIN 55672-1 (2016-03-01), using DMF as a fluid agent and PMMA as a standard, Thermoplastic polyurethane comprising at least components (a), (b), and (c): (a) at least one diisocyanate (I1), (b) at least one polyol composition (PC1), and (c) at least one chain extender (C1) Prepared by reacting, The polyol composition comprises at least one polyol (P1) and at least one component (CA1), The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. The polyol (P1) is a polyester polyol, and the component (CA1) is a polyester, preferably a cyclic polyester. method.

[0141] 45. Use of a composition according to any one of Embodiments 34 to 43 or a composition prepared according to the method described in Embodiment 44 for the manufacture of molded bodies, coatings, tubes, rolls, belts, damping elements, cable sheaths, hoses, films, nonwoven articles or fibers, foamed parts, particle foams, additive manufacturing filaments, 3D printing, extruded parts, and injection molded parts used in industrial applications, consumer goods including sports, automotive, agricultural, and construction applications.

[0142] 46. ​​At least components (i) and (ii): (i) A thermoplastic polyurethane which is a reaction product of at least one diisocyanate (I1), at least one polyol (P1), and at least one chain extender (C1), and (ii) Using DMF as a fluid agent and PMMA as a standard, at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, as determined by GPC in accordance with DIN 55672-1 (2016-03-01). A composition comprising, The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. The polyol (P1) is a polyether polyol, and the component (CA1) is a polyether, preferably a cyclic polyether. composition.

[0143] 47. The composition according to Embodiment 46, wherein the functional groups (F1) and (F2) are the same as each other.

[0144] 48. The composition according to Embodiment 46 or 47, wherein component (CA1) is a cyclic oligomer of ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, or 1,4-butylene oxide.

[0145] 49. The composition according to any one of embodiments 46 to 48, wherein the polyol (P1) is a polyether polyol selected from the group consisting of polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol.

[0146] 50. The composition according to any one of embodiments 46 to 49, wherein the chain extender (C1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, hexanediol, or mixtures thereof.

[0147] 51. The composition according to any one of Embodiments 46 to 50, wherein the isocyanate is selected from the group consisting of methylenediphenyl diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI), p-phenylenediisocyanate (PDI), 2,2'-diisocyanate (H12MDI), naphthylene 1,5-diisocyanate (NDI), isophorone diisocyanate (IPDI), and mixtures thereof.

[0148] 52. The composition according to any one of Embodiments 46 to 51, wherein the proportion of component (CA1) given as the content of the cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition.

[0149] 53. A composition according to any one of Embodiments 46 to 51, wherein the proportion of a component (CA1) given as the content of a cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition, the content of the migratory portion is determined using an injection molding plate, which is first stored at 100°C for 20 hours, and then the content of an oligomer with a molecular weight of 500 g / mol is determined by thermal desorption GC-MS similar to VDA 278 (FOG run only) with a desorption time of 60 minutes, the evaluation is performed using a total ion chromatogram (TIC), the content is calculated as hexadecane equivalent (ppmHdE), and the proportion of oligomers is determined by the peak size.

[0150] 54. The composition according to any one of Embodiments 46 to 53, wherein the proportion of thermoplastic polyurethane in the composition is in the range of 75% to 99.9% by weight relative to the whole composition.

[0151] 55. A method for preparing a composition comprising thermoplastic polyurethane and at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, determined by GPC in accordance with DIN 55672-1 (2016-03-01), using DMF as a fluid agent and PMMA as a standard, Thermoplastic polyurethane comprising at least components (a), (b), and (c): (a) at least one diisocyanate (I1), (b) at least one polyol composition (PC1), and (c) at least one chain extender (C1) Prepared by reacting, The polyol composition comprises at least one polyol (P1) and at least one component (CA1), The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. The polyol (P1) is a polyether polyol, and the component (CA1) is a polyether, preferably a cyclic polyether. method.

[0152] 56. Use of compositions according to any one of Embodiments 46 to 54 or compositions prepared according to the method described in Embodiment 55 for the manufacture of molded bodies, coatings, tubes, rolls, belts, damping elements, cable sheaths, hoses, films, nonwoven articles or fibers, foamed parts, particle foams, additive manufacturing filaments, 3D printing, extruded parts, and injection molded parts used in industrial applications, consumer goods including sports, automotive, agricultural, and construction applications.

[0153] 57. At least components (i) and (ii): (i) A thermoplastic polyurethane which is a reaction product of at least one diisocyanate (I1), at least one polyol (P1), and at least one chain extender (C1), and (ii) Using DMF as a fluid agent and PMMA as a standard, at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, as determined by GPC in accordance with DIN 55672-1 (2016-03-01). A composition comprising, The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. The proportion of the component (CA1) given as the content of the cyclic migration portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition. composition.

[0154] 58. At least components (i) and (ii): (i) A thermoplastic polyurethane which is a reaction product of at least one diisocyanate (I1), at least one polyol (P1), and at least one chain extender (C1), and (ii) Using DMF as a fluid agent and PMMA as a standard, at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, as determined by GPC in accordance with DIN 55672-1 (2016-03-01). A composition comprising, The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. The proportion of the component (CA1) given as the content of the cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the total composition. The content of the migratory portion is determined using an injection molding plate, which is first stored at 100°C for 20 hours. Then, the content of the oligomer with a molecular weight of 500 g / mol is determined by thermal desorption GC-MS similar to VDA 278 (FOG run only) with a desorption time of 60 minutes. Evaluation is performed using total ion chromatography (TIC), and the content is calculated as hexadecane equivalent (ppmHdE). The proportion of oligomers is determined by peak size. composition.

[0155] 59. The composition according to Embodiment 57 or 58, wherein the functional groups (F1) and (F2) are the same as each other.

[0156] 60. The composition according to any one of embodiments 57 to 59, wherein the polyol (P1) is a polyester polyol.

[0157] 61. A composition according to any one of embodiments 57 to 60, wherein component (CA1) is polyester, preferably a cyclic polyester.

[0158] 62. The composition according to any one of Embodiments 57 to 61, wherein component (CA1) is a polyester which is a reaction product of a dicarboxylic acid (a1) and a diol (d1), the dicarboxylic acid (a1) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

[0159] 63. The composition according to Embodiment 62, wherein a mixture of two diols selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol is used as diol (d1).

[0160] 64. The composition according to any one of Embodiments 57 to 63, wherein the polyol is a polyester polyol which is a reaction product of a dicarboxylic acid (a2) and a diol (d2), the dicarboxylic acid (a2) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d2) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

[0161] 65. The composition according to any one of embodiments 57 to 59, wherein the polyol (P1) is a polyether polyol.

[0162] 66. A composition according to any one of embodiments 57 to 65, wherein component (CA1) is a polyether, preferably a cyclic polyether.

[0163] 67. The composition according to any one of embodiments 57 to 66, wherein component (CA1) is a cyclic oligomer of ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, or 1,4-butylene oxide.

[0164] 68. The composition according to any one of embodiments 57 to 67, wherein the polyol (P1) is a polyether polyol selected from the group consisting of polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol.

[0165] 69. The composition according to any one of embodiments 57 to 68, wherein the chain extender (C1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, hexanediol, or mixtures thereof.

[0166] 70. A composition according to any one of Embodiments 57 to 69, wherein the isocyanate is selected from the group consisting of methylenediphenyl diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI), p-phenylenediisocyanate (PDI), 2,2'-diisocyanate (H12MDI), naphthylene 1,5-diisocyanate (NDI), isophorone diisocyanate (IPDI), and mixtures thereof.

[0167] 71. The composition according to any one of Embodiments 57 to 70, wherein the proportion of component (CA1) given as the content of the cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition.

[0168] 72. The composition according to any one of Embodiments 57 to 71, wherein the proportion of thermoplastic polyurethane in the composition is in the range of 75% to 99.9% by weight relative to the whole composition.

[0169] 73. A method for preparing a composition comprising thermoplastic polyurethane and at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, determined by GPC in accordance with DIN 55672-1 (2016-03-01), using DMF as a fluid agent and PMMA as a standard, Thermoplastic polyurethane comprising at least components (a), (b), and (c): (a) at least one diisocyanate (I1), (b) at least one polyol composition (PC1), and (c) at least one chain extender (C1) Prepared by reacting, The polyol composition comprises at least one polyol (P1) and at least one component (CA1), The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and component (CA1) contains a functional group (F2) selected from ether groups and ester groups. The proportion of the component (CA1) given as the content of the cyclic migration portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition. method.

[0170] 74. Use of compositions according to any one of Embodiments 57 to 72 or compositions prepared according to the method described in Embodiment 73 for the manufacture of molded bodies, coatings, tubes, rolls, belts, damping elements, cable sheaths, hoses, films, nonwoven articles or fibers, foamed parts, particle foams, additive manufacturing filaments, 3D printing, extruded parts, and injection molded parts used in industrial applications, consumer goods including sports, automotive, agricultural, and construction applications. [Examples]

[0171] 1.Material The following materials: Polyol A: A polyester polyol purified in a separate process, with an OH value of 35.9 and containing only primary OH groups (based on 1,2-ethanediol and 1,4-butanediol (in a 1:1 ratio), and adipic acid, with a functional value of 2). Polyol B: A polyester polyol with an OH value of 35.9 and containing only primary OH groups (based on 1,2-ethanediol and 1,4-butanediol (in a 1:1 ratio), and adipic acid, with a functional value of 2). Polyol C: A polyester polyol purified in a separate process, with an OH value of 56.1 and containing only primary OH groups (based on 1,2-ethanediol and 1,4-butanediol (in a 1:1 ratio), and adipic acid, with a functional value of 2). Polyol D: An OH value of 56.1, a polyester polyol having only primary OH groups (based on 1,2-ethanediol and 1,4-butanediol (in a 1:1 ratio), and adipic acid, with a functional value of 2). Polyol E: An OH value of 36.5, a polyester polyol having only primary OH groups (based on 1,6-hexanediol and 1,4-butanediol (in a 1:1 ratio), and adipic acid, with a functional value of 2). Polyol F: An OH value of 56.0, a polyether polyol (based on tetramethylene oxide, with a functional value of 2) containing only primary OH groups. Polyol G: An OH value of 112.0, a polyether polyol (based on tetramethylene oxide, with a functional value of 2) containing only primary OH groups. Diisocyanate 1: Aromatic isocyanate (4,4'-methylenediphenyl diisocyanate) KV1: 1,4-butanediol Stabilizer 1: High molecular weight carbodiimide Catalyst: Titanium(IV) butoxide (TTB), CAS: 5593-70-4 2-Tin(II) ethylhexanoate (SDO), CAS: 301-10-0 I used it.

[0172] 2. Preparation of ester polyols 2.1 Polyol A 611.97 kg of adipic acid, 138.24 kg of monoethylene glycol, 200.71 kg of 1,4-butanediol, and 1 ppm of TTB are placed in a 1000-liter stainless steel reactor equipped with an oil heater, temperature controller, nitrogen inlet, distillation column, and stirrer. The reactor is preheated to approximately 80°C, and the raw materials are added while the stirrer is running. The target temperature is set to 240°C. As the reaction proceeds, water is released and removed through the column. After the distillate reaches 80% of the calculated nominal amount, 5 ppm of SDO is added, and the pressure is reduced to 60 mbar within 1 hour. The formed reaction water is continuously removed by distillation until the acid value (AN) reaches less than 0.6 mg KOH / g.

[0173] A polyester polyol with a hydroxyl value of 38 mg KOH / g, an acid value of 0.5 mg KOH / g, and a viscosity of 1550 mPas at 75°C is obtained.

[0174] Next, polyol A was purified using a thin-film evaporator (DSV). For this purpose, the polyol was heated to 120°C and metered and supplied to the DSV using a gear pump. The DSV was adjusted to 240°C at a speed of 400 rpm. Simultaneously, a vacuum of less than 5 mbar was applied. The feeding rate was approximately 1 kg / h.

[0175] 2.2 Polyol B 611.97 kg of adipic acid, 138.24 kg of monoethylene glycol, 200.71 kg of 1,4-butanediol, and 1 ppm of TTB are placed in a 1000-liter stainless steel reactor equipped with an oil heater, temperature controller, nitrogen inlet, distillation column, and stirrer. The reactor is preheated to approximately 80°C, and the raw materials are added while the stirrer is running. The target temperature is set to 240°C. As the reaction proceeds, water is released and removed through the column. After the distillate reaches 80% of the calculated nominal amount, 5 ppm of SDO is added, and the pressure is reduced to 60 mbar within 1 hour. The formed reaction water is continuously removed by distillation until the AN reaches less than 0.6 mg KOH / g.

[0176] A polyester polyol with a hydroxyl value of 38 mg KOH / g, an acid value of 0.5 mg KOH / g, and a viscosity of 1550 mPas at 75°C is obtained.

[0177] 2.3 Polyol C 1656.75 g of adipic acid, 756.08 g of 1,4-butanediol, and 495.75 g of 1,6-hexanediol are placed in a 4-liter round-bottom flask equipped with a thermometer, nitrogen inlet, heating mantle, distillation column, condenser, and stirrer, and heated to 120°C. After the adipic acid and 1,6-hexanediol have completely dissolved, the stirrer is operated at a speed of 200 rpm and the temperature is set to 180°C. After reaching 180°C and removing the already formed reaction water, the temperature is set to 240°C and further reaction water is removed. After 90% of the calculated condensate has been separated and the temperature has reached 240°C, 10 ppm of SDO is metered in and the pressure in the apparatus is reduced to 60 mbar. The formed condensate is continuously removed until the acid value reaches less than 0.6 mg KOH / g. A polyol having a hydroxyl value of 56 mg KOH / g and an acid value of 0.6 mg KOH / g is obtained.

[0178] Next, the polyol was purified using a thin-film evaporator (DSV). For this purpose, the polyol was heated to 120°C and metered into the DSV using a gear pump. The DSV was heated to 240°C at a speed of 400 rpm. Simultaneously, a vacuum of less than 5 mbar was applied. The feeding rate was approximately 1 kg / h. Polyol C with a hydroxyl value of 51 mg KOH / g and an acid value of 0.6 mg KOH / g was obtained.

[0179] 2.4 Polyol D 1656.75 g of adipic acid, 756.08 g of 1,4-butanediol, and 495.75 g of 1,6-hexanediol are placed in a 4-liter round-bottom flask equipped with a thermometer, nitrogen inlet, heating mantle, distillation column, condenser, and stirrer, and heated to 120°C. After the adipic acid and 1,6-hexanediol have completely dissolved, the stirrer is operated at a speed of 200 rpm and the temperature is set to 180°C. After reaching 180°C and removing the already formed reaction water, the temperature is set to 240°C and further reaction water is removed. After 90% of the calculated condensate has been separated and the temperature has reached 240°C, 10 ppm of SDO is metered in and the pressure in the apparatus is reduced to 60 mbar. The formed condensate is continuously removed until the acid value reaches less than 0.6 mg KOH / g. Polyol D is obtained having a hydroxyl value of 56 mg KOH / g and an acid value of 0.6 mg KOH / g.

[0180] 2.5 Polyol E 1656.75 g of adipic acid, 558.6 g of 1,4-butanediol, and 558.6 g of 1,6-2-methylpropane-1,3-diol are placed in a 4-liter round-bottom flask equipped with a thermometer, nitrogen inlet, heating mantle, distillation column, condenser, and stirrer, and heated to 120°C. After the adipic acid has completely dissolved, the stirrer is operated at a speed of 200 rpm and the temperature is set to 180°C. After reaching 180°C and removing the already formed reaction water, the temperature is set to 240°C and further reaction water is removed. After 90% of the calculated condensate has been separated and the temperature has reached 240°C, 10 ppm of SDO is metered in and the pressure in the apparatus is reduced to 60 mbar. The formed condensate is continuously removed until the acid value reaches less than 0.6 mg KOH / g. Polyol E is obtained having a hydroxyl value of 37.4 mg KOH / g and an acid value of 0.6 mg KOH / g.

[0181] 2.12 Polyol F PolyTHF is produced by polymerizing THF in the presence of acetic anhydride (ESA). For this purpose, THF and ESA are continuously supplied to the polymerization reactor in a specified ratio of 0.03 to 0.04. In the reactor, at a temperature of approximately 40°C, polyTHF diacetate is formed as a precursor of polyTHF on a fixed-bed catalyst made of activated alumina. After separating the unreacted THF, the crude polyTHF diacetate is converted to polyTHF by transesterification using excess methanol, catalyzed by sodium methoxide at a temperature of approximately 70 to 80°C (under an overpressure of approximately 100 mbar). This also produces methyl acetate (methyl ethyl acetate), which is removed from the transesterification equilibrium by distillation. After equilibrium is reached, the transesterified material is sent for neutralization with an acidic ion exchanger. In further processing, excess methanol is removed by evaporation. To adjust the average molar mass or molecular weight distribution, the low molecular weight fraction (polyTHF oligomer) is evaporated from the polyTHF.

[0182] 2.13 Polyol G PolyTHF is produced by polymerizing THF in the presence of acetic anhydride (ESA). For this purpose, THF and ESA are continuously supplied to the polymerization reactor in a specified ratio of 0.03 to 0.04. In the reactor, at a temperature of approximately 40°C, polyTHF diacetate is formed as a precursor of polyTHF on a fixed-bed catalyst made of activated alumina. After separating the unreacted THF, the crude polyTHF diacetate is converted to polyTHF by transesterification using excess methanol, catalyzed by sodium methoxide at a temperature of approximately 70 to 80°C (under an overpressure of approximately 100 mbar). This also produces methyl acetate (methyl ethyl acetate), which is removed from the transesterification equilibrium by distillation. After equilibrium is reached, the transesterified material is sent for neutralization with an acidic ion exchanger. In further processing, excess methanol is removed by evaporation. To adjust the average molar mass or molecular weight distribution, the low molecular weight fraction (polyTHF oligomer) is evaporated from the polyTHF.

[0183] 3. Method: 3.1 Viscosity Unless otherwise specified, the viscosity of polyols was determined at 25°C in accordance with DIN EN ISO 3219 (1994) using a Rheotec RC 20 rotational viscometer with a CC 25 DIN spindle (spindle diameter: 12.5 mm; graduated cylinder inner diameter: 13.56 mm) at a shear rate of 50 1 / s.

[0184] 3.2 OH value The hydroxyl value was determined using the acetic anhydride method DIN 53240 (1971-12) and is expressed in mgKOH / g.

[0185] 3.3 Acid value The acid value is determined in accordance with DIN EN 1241 (1998-05) and expressed in mgKOH / g.

[0186] 3.4 Determination of low molecular weight by-products in polyols The amount of low molecular weight by-products in the polyol was determined by GPC in accordance with DIN 55672-1 (2016-03-01), using THF as a fluidizing agent and PEG as a standard for detecting oligomers less than 500 g / mol. Differentiation from additives was performed using a UV detector at a wavelength of 254 nm, and oligomer detection was performed using a refractive index (RI) detector.

[0187] In addition, the proportion of oligomers less than 500 g / mol was determined by weighing 2-4 mg at 120°C for 10 minutes using thermal desorption GC-MS in accordance with VDA 278 (FOG run only). Evaluation was performed using total ion chromatography (TIC). The obtained values ​​were calculated as hexadecane equivalents (ppmHdE). The monocyclic (ADS glycol) fraction was determined by peak size. In the case of ether polyols, calibration was performed against a THF-based crown ether with n=4.

[0188] [Table 1]

[0189] 4.TPU synthesis: Thermoplastic polyurethane (TPU) was synthesized from diisocyanate, chain extender (KV), stabilizer, and polyol according to the formulation in Table 2, with stirring in a reaction vessel. The starting temperature was 80°C. After reaching a reaction temperature of 110°C, the solution was poured onto a heating plate heated to 125°C, and the resulting TPU plate was tempered (15 hours, 80°C) and then granulated.

[0190] Hard segment content (HSC) is defined as follows: M KVx : Molar mass of chain extender x in units of g / mol m KVx : Mass of chain extender x in grams M Iso Molar mass of isocyanate using g / mol units m ges : Total mass of all starting materials in grams x: Number of chain extenders The following expression has

number

[0191] [Table 2]

[0192] 5. Characteristics of TPUs Blooming behavior was analyzed using alternating climate tests and storage under standard climate conditions on untempered 2 mm thick injection-molded sheets. For the alternating climate test, samples were stored alternately at -18°C and room temperature (25°C) for 12 hours each over a two-week period. The results are summarized in Table 3.

[0193] Blooming / migration characteristics were evaluated using surface optics. The intensity of the white crystalline deposits was visually assessed. The obtained blooming / migration characteristics of the TPU were: +=Good (no visible deposits) o = Moderate (only pinpoint / stain-like deposits) -=Defective (deposits across the entire surface) --=Extremely poor condition (severe deposition across the entire surface) They were classified as follows.

[0194] The processability in injection molding was tested using a DEMAG ergotech 200 / 500-610 injection molding machine with a φ40mm 3-zone screw. To do this, TPU granules, free from any other release agents such as wax or soap, were first dried at 90°C for 3 hours. The processing temperature for each screw zone was 190°C to 230°C. Meanwhile, a cylinder with a wall thickness of 8mm (outer diameter φ80mm, depth 40mm) was fabricated as an injection molded part in the jaw mold. It was injected into an octave cold runner star submanifold using an open hot runner nozzle. Meanwhile, a disc (φ125mm, thickness 27mm) was fabricated as an additional injection molded part in the jaw mold. Gating was performed via a central cold runner sprue. Demolding was performed via a ring ejector that removed the sleeve from the core located in the cavity for demolding. A force sensor on the ejector system transmitted the force required to remove the case. +=Good (<13000N) -=Bad (>13000N)

[0195] In addition, the production of expanded particle foam (eTPU) in an extrusion process (disclosed, for example, in International Publication No. 2013 / 153190) was tested, and the blocking properties of eTPU obtained in a 200 L octabine were observed after 2 months of storage at room temperature. +=Good (eTPU foam beads were individual) o = moderate (The eTPU foam beads were slightly stuck together, but could be separated again with a light touch) -=Defective (The foam beads are stuck together, so when you tilt the octabine to empty the contents, you can also see clumps of stuck foam beads.)

[0196] Cold flex was measured using dynamic mechanical analysis (DMA) in accordance with DIN EN ISO 6721-1:2011-08 on specimens tempered at 100°C for 20 hours at a heating rate of 2 K / min and a frequency of 1 Hz determined under torsion. Here, the maximum value of the loss factor (tanδ) was evaluated as "+" above -25°C and "-" below -25°C.

[0197] Soft phase crystallization was determined by differential scanning calorimetry (DSC) in accordance with DIN EN ISO 11357-3:2013 at a heating rate of 20°C / min on injection-molded plates tempered at 100°C for 20 hours. Prior to DSC measurement, the TPU was dried at 100°C for 10 minutes. If an exothermic melting peak with a maximum value of less than 40°C was present during the first heating run, the sample was evaluated as "-"; otherwise, it was evaluated as "+".

[0198] [Table 3]

[0199] The mechanical properties of the obtained thermoplastic polyurethanes are shown in Table 4. The mechanical properties were determined at room temperature using the following method on a 2 mm thick injection-molded plate tempered at 100°C for 20 hours. Shore hardness is determined according to DIN ISO 7619-1:2012 after a 3-second press-fit time. Tensile strength DIN 53504:2017-03, S2 specimen, speed 200 mm / min Elongation at break: DIN 53504:2017-03, S2 specimen, speed 200 mm / min

[0200] [Table 4]

[0201] 6. Determination of the low molecular weight fraction in TPU The proportion of the low molecular weight fraction was quantitatively analyzed by GPC at a flow rate of 1.50 mL / min using dimethylformamide (DMF) as the eluent. The solution was calibrated against a congener of polymethyl methacrylate using a PSS SDV linear XL 5 μm column and toluene as the standard.

[0202] Injection-molded plates were first stored at 100°C for 20 hours. Then, oligomer content less than 500 g / mol was determined by thermal desorption GC-MS similar to VDA 278 (FOG run only) with a desorption time of 60 minutes. Evaluation was performed using total ion chromatography (TIC). The obtained values ​​were calculated as hexadecane equivalents (ppmHdE). The proportion of monocyclic molecules (consisting of ADS and 1,4-butanediol), or in the case of ethers, the proportion of crown ethers consisting of three THF molecules, was determined by peak size.

[0203] [Table 5]

[0204] References: International Publication No. 15 / 000722 International Publication No. 2019 / 002263 European Patent Application Publication No. 0687695 International Publication No. 2012 / 173911 U.S. Patent Application Publication No. 2003 / 0036621 International Publication No. 2009 / 103767 International Publication No. 94 / 20568 International Publication No. 2007 / 082838 International Publication No. 2017 / 030835 International Publication No. 2013 / 153190 International Publication No. 2010 / 010010 “Plastics Handbook, volume 7, Polyurethanes [Polyurethanes]”, Carl Hanser Verlag, 3rd edition 1993, chapter 3.1 Plastics Handbook, volume VII, edited by Vieweg and Hoechtlen, Carl Hanser Verlag, Munich 1966 (p. 103-113)

Claims

1. At least components (i) and (ii): (i) A thermoplastic polyurethane which is a reaction product of at least one diisocyanate (I1), at least one polyol (P1), and at least one chain extender (C1), and (ii) At least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, determined by GPC in accordance with DIN 55672-1 (2016-03-01), using DMF as a fluid agent and PMMA as a standard. A composition comprising, The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and the component (CA1) contains a functional group (F2) selected from ether groups and ester groups, wherein the functional groups (F1) and (F2) are the same as each other. composition.

2. The composition according to claim 1, wherein (F1) and (F2) are ether groups, or (F1) and (F2) are ester groups.

3. The composition according to claim 1 or 2, wherein the polyol (P1) is a polyester polyol.

4. The composition according to any one of claims 1 to 3, wherein the component (CA1) is polyester, preferably a cyclic polyester.

5. The composition according to any one of claims 1 to 4, wherein the component (CA1) is a polyester which is a reaction product of a dicarboxylic acid (a1) and a diol (d1), the dicarboxylic acid (a1) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

6. The composition according to claim 5, wherein a mixture of two diols selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol is used as the diol (d1).

7. The composition according to any one of claims 1 to 6, wherein the polyol is a polyester polyol which is a reaction product of a dicarboxylic acid (a2) and a diol (d2), the dicarboxylic acid (a2) is selected from the group consisting of adipic acid, succinic acid, or mixtures thereof, and the diol (d2) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, and hexanediol, or mixtures thereof.

8. The composition according to claim 1 or 2, wherein the polyol (P1) is a polyether polyol.

9. The composition according to any one of claims 1 to 8, wherein the component (CA1) is a polyether, preferably a cyclic polyether.

10. The composition according to any one of claims 1 to 9, wherein the component (CA1) is a cyclic oligomer of ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, or 1,4-butylene oxide.

11. The composition according to any one of claims 1 to 10, wherein the polyol (P1) is a polyether polyol selected from the group consisting of polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol.

12. The composition according to any one of claims 1 to 11, wherein the chain extender (C1) is selected from the group consisting of ethanediol, propanediol, butanediol, pentanediol, hexanediol, or mixtures thereof.

13. The composition according to any one of claims 1 to 12, wherein the isocyanate is selected from the group consisting of methylenediphenyl diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI), p-phenylenediisocyanate (PDI), 2,2'-diisocyanate (H12MDI), naphthylene 1,5-diisocyanate (NDI), isophorone diisocyanate (IPDI), and mixtures thereof.

14. The composition according to any one of claims 1 to 13, wherein the proportion of component (CA1) given as the content of the cyclic migratory portion in the composition is in the range of 55 to 280 ppmHde by weight relative to the whole composition.

15. The composition according to any one of claims 1 to 14, wherein the proportion of the thermoplastic polyurethane in the composition is in the range of 75% to 99.9% by weight relative to the whole composition.

16. A method for preparing a composition comprising a thermoplastic polyurethane and at least one component (CA1) having a molecular weight Mn in the range of 50 to 500 g / mol, determined by GPC in accordance with DIN 55672-1 (2016-03-01), using DMF as a fluid agent and PMMA as a standard, The thermoplastic polyurethane comprises at least components (a), (b), and (c): (a) at least one diisocyanate (I1) (b) at least one polyol composition (PC1), and (c) at least one chain extender (C1) Prepared by reacting, The polyol composition comprises at least one polyol (P1) and at least one component (CA1), The polyol (P1) contains a functional group (F1) selected from ether groups and ester groups in its polymer backbone, and the component (CA1) contains a functional group (F2) selected from ether groups and ester groups. method.

17. Use of the composition according to any one of claims 1 to 15 or a composition prepared according to the method according to claim 16 for the manufacture of molded bodies, coatings, tubes, rolls, belts, damping elements, cable sheaths, hoses, films, nonwoven articles or fibers, foamed parts, particle foams, additive manufacturing filaments, 3D printing, extruded parts, and injection molded parts used in industrial applications, consumer goods including sports, automotive, agricultural, and construction applications.

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