Hard Phase Modified Thermoplastic Polyurethanes

Abstract

The present invention relates to a thermoplastic polyurethane obtainable or obtained by a process comprising reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1), and reacting the resulting composition (Z1) with an isocyanate composition (I1) comprising at least one polyisocyanate and a polyol composition (P1), wherein the diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol. The present invention further relates to a process for producing such a thermoplastic polyurethane, and to a molded article comprising the thermoplastic polyurethane according to the invention.

Description

[Technical field]

[0001] The present invention relates to a thermoplastic polyurethane obtainable or obtained by a process comprising reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1), and reacting the composition (Z1) obtained with an isocyanate composition (I1) comprising at least one polyisocyanate and a polyol composition (P1), wherein the diamine (D1) has a molecular weight in the range from 50 g / mol to 700 g / mol. The present invention further relates to a process for the preparation of such a thermoplastic polyurethane and to a moulded article comprising a thermoplastic polyurethane according to the invention. [Background technology]

[0002] Thermoplastic polyurethanes are well known for their excellent mechanical properties, high abrasion resistance and high elasticity. They are therefore used in a very wide range of applications. Thermoplastic polyurethanes are also widely used in the automotive sector. Individual applications, for example charging cables for hybrid and electric vehicles, require high thermal stability. The standards that apply to cables for automotive applications are LV 112 and ISO 6722, which classify materials according to specific temperature classes.

[0003] For new applications, manufacturers often select temperature class D cables, suitable for temperatures up to 150°C in applications close to the engine. Examples include engine wiring harnesses or transmission connections. Electric and hybrid vehicles place particularly high demands on wiring harnesses and conduits that have limited similarity to previously customary on-board electrical systems. These cables therefore need to withstand significantly higher temperatures than conventional cables as a result of high voltages of up to 1000V and corresponding high currents. The cables must withstand normal winding tests after 3000 hours of hot air aging at 150°C.

[0004] In temperature class D (up to 150 °C), in particular ethylene-tetrafluoroethylene copolymers (ETFE) are used, however, the use of these materials is often restricted because ETFE gives off corrosive gases in case of fire.

[0005] Certain crosslinked polyolefin compounds are further materials. However, they can only be produced in a very complicated and costly manner, since they require subsequent crosslinking by irradiation or vulcanization, and they often reach their limits in terms of chemical resistance and low mechanical elasticity. In addition, crosslinked materials have the disadvantage that they cannot be recycled and cause watertightness problems when molding plugs and grommets.

[0006] The currently widely used standard LV 112 also has strict requirements for hydrolysis resistance at high temperatures: ISO 6722 requires a service life of 1000-3000 hours at 85°C and 85% relative humidity, while LV 112 requires a service life of 3000 hours.

[0007] The remaining requirements for the cable sheath are nearly identical in both standards and are standard among the materials currently sold for this purpose. These requirements include cold resistance, media resistance, inhibition of mold growth, and compatibility with further materials in the wire harness, such as adhesive tapes, shrink tubing, connectors, etc.

[0008] However, for many applications, no materials exist that combine good mechanical properties with the unique demands of automotive applications, and many conventional thermoplastic polyurethanes degrade under these stresses. Summary of the Invention [Problem to be solved by the invention]

[0009] It is therefore an object of the present invention to provide a thermoplastic polyurethane that exhibits good mechanical properties and high thermal stability. [Means for solving the problem]

[0010] According to the invention, this object is achieved by a thermoplastic polyurethane obtainable or obtained by a process comprising the reaction of an isocyanate composition (I1) comprising at least one polyisocyanate with a polyol composition (P1), in which at least one diamine (D1) having a molecular weight in the range from 50 g / mol to 700 g / mol is used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] According to the invention, the diamine (D1) may be used as such in the process, for example as a chain extender, or may be reacted with a thermoplastic polyester (PE-1) to give an amide (PA-1), prior to the reaction of the isocyanate composition (I1) with the polyol composition (P1).

[0012] Thus, in a further embodiment, the present invention also provides a thermoplastic polyurethane as described above, wherein the diamine D1 is reacted with the thermoplastic polyester (PE-1) to obtain the amide (PA-1) prior to the reaction of the isocyanate composition (I1) with the polyol composition (P1).

[0013] Thus, according to the invention, this object is also achieved by a thermoplastic polyurethane obtainable or obtained by a process comprising the reaction of an isocyanate composition (I1) comprising at least one polyisocyanate with a polyol composition (P1), in which at least one diamine (D1) having a molecular weight in the range of 50 g / mol to 700 g / mol is reacted with a thermoplastic polyester (PE-1) prior to the reaction of the isocyanate composition (I1) with the polyol composition (P1) to obtain an amide (PA-1).

[0014] Thus, the present invention relates to a process for producing a method for producing a compound comprising the steps (i) and (ii): (i) reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1); (ii) reacting the composition (Z1) obtained according to step (i) with an isocyanate composition (I1) comprising at least one polyisocyanate and with a polyol composition (P1); Also provided is a thermoplastic polyurethane obtainable or obtained by a process comprising: Here, the diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol.

[0015] In an alternative embodiment, the present invention also provides a thermoplastic polyurethane as described above, wherein a diamine (D1) is used as a chain extender.

[0016] Thus, in a further embodiment, the present invention also provides a thermoplastic polyurethane as described above, wherein the process comprises the step of: (a) an isocyanate composition (I1) comprising at least one polyisocyanate; (b) a polyol composition (P1), and (c) diamines (D1) as chain extenders, This includes reactions such as:

[0017] When diamines (D1) are used as chain extenders, the process may be carried out under conditions commonly used. Particularly suitable chain extenders are diamines (D1) selected from the compounds of general formula (I) or (II): [ka] wherein R1 and R2 are independently selected from the group consisting of O-CH3, CH2CH3, S-CH3, NH-CH3, N(CH3)2 and H, or [ka] (In the formula, a) X1 = X2 = Y1 = Y2 = H, b) X1 = X2 = Y1 = Y2 = CH3; c) X1 = X2 = Y1 = Y2 = isopropyl; d) X1 = X2 = Y1 = Y2 = C2H5; e) X1 = X2 = Y1 = Y2 = butyl; f) X1 = X2 = Y1 = Y2 = tert-butyl; g) X1=X2=H and Y1=Y2=CH3, h) X1=X2=H, and Y1=Y2=isopropyl; i) X1=X2=H and Y1=Y2=C2H5; j) X1=X2=H and Y1=Y2=butyl, or k) X1=X2=H, and Y1=Y2=tert-butyl; Z is selected from the group consisting of CH2, CHCH3, C(CH3)2, O and S.

[0018] The present invention therefore also provides a thermoplastic polyurethane obtainable or obtained by a process comprising the reaction of an isocyanate composition (I1) comprising at least one polyisocyanate with a polyol composition (P1), in which at least one diamine (D1) is used having a molecular weight ranging from 50 g / mol to 700 g / mol and selected from compounds of general formula (I) or (II): [ka] wherein R1 and R2 are independently selected from the group consisting of O-CH3, CH2CH3, S-CH3, NH-CH3, N(CH3)2 and H, or [ka] (In the formula, a) X1 = X2 = Y1 = Y2 = H, b) X1 = X2 = Y1 = Y2 = CH3; c) X1 = X2 = Y1 = Y2 = isopropyl; d) X1 = X2 = Y1 = Y2 = C2H5; e) X1 = X2 = Y1 = Y2 = butyl; f) X1 = X2 = Y1 = Y2 = tert-butyl; g) X1=X2=H and Y1=Y2=CH3, h) X1=X2=H, and Y1=Y2=isopropyl; i) X1=X2=H and Y1=Y2=C2H5; j) X1=X2=H and Y1=Y2=butyl, or k) X1=X2=H, and Y1=Y2=tert-butyl; Z is selected from the group consisting of CH2, CHCH3, C(CH3)2, O and S.

[0019] In one embodiment, the process according to the invention comprises in particular steps (i) and (ii). In step (i), a thermoplastic polyester (PE-1) is reacted with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1), where the diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol. In step (ii) of the process according to the invention, the composition (Z1) obtained according to step (i) is reacted with an isocyanate composition (I1) comprising at least one polyisocyanate and a polyol composition (P1).

[0020] The process mode according to the invention makes it possible to obtain thermoplastic polyurethanes containing modified hard phases. Surprisingly, it has been found that the stepwise reaction of these components makes it possible to obtain thermoplastic polyurethanes that exhibit good mechanical properties and high thermal stability. This makes them particularly suitable for use as cable sheaths. It is further advantageous for many applications in the field of cable sheaths that the moldings produced from the thermoplastic polyurethanes according to the invention by extrusion or injection molding exhibit a matte surface.

[0021] The reaction according to step (i) is preferably carried out continuously. Thus, in a further embodiment, the present invention provides a process for the preparation of a thermoplastic polyurethane as described above, wherein the reaction according to step (i) is carried out continuously.

[0022] According to step (i), the thermoplastic polyester (PE-1) is reacted with a diamine (D1), which in the context of the present invention forms an amide. The diamine (D1) may in principle be selected from any commonly used diamine having a molecular weight in the range of 50 g / mol to 700 g / mol, preferably in the range of 50 to 500 g / mol. For example, aliphatic or aromatic diamines are suitable. According to the present invention, aromatic diamines are preferred.

[0023] It has proven to be particularly advantageous to use diamines having an aromatic structure. Preferably used in the context of the present invention are diamines (D1) selected from the compounds of general formula (I) or (II): [ka] wherein R1 and R2 are independently selected from the group consisting of O-CH3, CH2CH3, S-CH3, NH-CH3, N(CH3)2 and H; or [ka] (In the formula, a) X1 = X2 = Y1 = Y2 = H, b) X1 = X2 = Y1 = Y2 = CH3; c) X1 = X2 = Y1 = Y2 = isopropyl; d) X1 = X2 = Y1 = Y2 = C2H5; e) X1 = X2 = Y1 = Y2 = butyl; f) X1 = X2 = Y1 = Y2 = tert-butyl; g) X1=X2=H and Y1=Y2=CH3, h) X1=X2=H, and Y1=Y2=isopropyl; i) X1=X2=H and Y1=Y2=C2H5; j) X1=X2=H and Y1=Y2=butyl, or k) X1=X2=H, and Y1=Y2=tert-butyl; Z is selected from the group consisting of CH2, CHCH3, C(CH3)2, O and S.

[0024] Thus, in a further embodiment, the present invention provides a thermoplastic polyurethane as described above, wherein the diamine (D1) is selected from the compounds of general formula (I) or (II): [ka] wherein R1 and R2 are independently selected from the group consisting of O-CH3, CH2CH3, S-CH3, NH-CH3, N(CH3)2 and H; or [ka] (In the formula, a) X1 = X2 = Y1 = Y2 = H, b) X1 = X2 = Y1 = Y2 = CH3; c) X1 = X2 = Y1 = Y2 = isopropyl; d) X1 = X2 = Y1 = Y2 = C2H5; e) X1 = X2 = Y1 = Y2 = butyl; f) X1 = X2 = Y1 = Y2 = tert-butyl; g) X1=X2=H and Y1=Y2=CH3, h) X1=X2=H, and Y1=Y2=isopropyl; i) X1=X2=H and Y1=Y2=C2H5; j) X1=X2=H and Y1=Y2=butyl, or k) X1=X2=H, and Y1=Y2=tert-butyl; Z is selected from the group consisting of CH2, CHCH3, C(CH3)2, O and S.

[0025] In the context of the present invention it is particularly preferable to use diamines (D1) having the general formula (III): [ka] (Wherein, R1=R2=S-CH3 or R1=R2=CH2CH3).

[0026] Thus, in a further embodiment, the present invention provides a thermoplastic polyurethane as described above, wherein the diamine (D1) has the general formula (III): [ka] (Wherein, R1=R2=S-CH3 or R1=R2=CH2CH3).

[0027] In the context of the present invention, mixtures of the abovementioned diamines may also be used.

[0028] According to step (i), a thermoplastic polyester (PE-1) is used. Thermoplastic polyesters suitable according to the invention are known per se. Suitable polyesters consist of at least one dicarboxylic acid and at least one suitable dihydroxy compound. The polyesters can be prepared, for example, by polycondensation of aliphatic or aromatic dicarboxylic acids or mixtures of aromatic and aliphatic and / or cycloaliphatic dicarboxylic acids with the corresponding ester-forming derivatives, such as dicarboxylic anhydrides, advantageously mono- and / or diesters having up to 4 carbon atoms in the alcohol radical, with aliphatic dihydroxy compounds at elevated temperatures, for example 160°C to 260°C, in the presence or absence of an esterification catalyst.

[0029] According to the invention, aromatic dicarboxylic acids, such as naphthalenedicarboxylic acid, isophthalic acid and especially terephthalic acid, or mixtures of these dicarboxylic acids, are preferred. Also suitable in the context of the invention are aliphatic and / or cycloaliphatic dicarboxylic acids, for example having 4 to 14 carbon atoms, such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and / or cyclohexanedicarboxylic acid.

[0030] Also according to the invention, polyester functionalized dicarboxylic acids, such as polyesters based on lactic acid, can be used.

[0031] In the context of the present invention, aliphatic or aromatic dihydroxy compounds can be used as further synthesis components of the thermoplastic polyester (PE-1). The aliphatic dihydroxy compounds expected are preferably alkanediols having 2 to 6 carbon atoms and cycloalkanediols having 5 to 7 carbon atoms. For example, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, or a mixture of at least two of the above-mentioned diols are preferably used.

[0032] Particularly suitable thermoplastic polyesters are those selected from the group consisting of polyalkylene terephthalates and poly-L-lactic acid.

[0033] In a further embodiment, the present invention also provides the above thermoplastic polyurethane, wherein the thermoplastic polyester (PE-1) is selected from the group consisting of polyalkylene terephthalate and poly-L-lactic acid.

[0034] According to the present invention, the molecular weight (Mn) of the polyester used is preferably in the range of 2,000 to 100,000, and more preferably in the range of 10,000 to 50,000.

[0035] In a further embodiment, the present invention also provides the above thermoplastic polyurethane, wherein the thermoplastic polyester (PE-1) has a molecular weight in the range of 1000 g / mol to 60000 g / mol, such as also in the range of 1500 g / mol to 5000 g / mol.

[0036] In the context of the present invention, the determination of the weight average molecular weight Mw of thermoplastic polyesters is carried out by GPC, unless otherwise stated, dissolved in HFIP (hexafluoroisopropanol). The molecular weight is determined using two GPC columns (PSS-Gel; 100A; 5μ; 300*8mm, Jordi-Gel DVB; mixed bed; 5μ; 250*10mm; column temperature 60°C; flow rate 1ml / min; RI detector) arranged in series. Here, calibration is carried out with polymethylmethacrylate (EasyCal; PSS, Mainz) and HFIP is used as the eluent.

[0037] For example, the proportion of diamine based on the polyester used may range from 5% to 20%.

[0038] Step (i) results in a composition (Z1) comprising amide (PA-1). In the context of the present invention, composition (Z1) may also comprise further components, such as unconverted thermoplastic polyester or unconverted diamine. Typically, composition (Z1) is a mixture that may also comprise unconverted polyester (PE-1) or unreacted diamine in addition to amide (PA-1). Thus, according to the present invention, amide (PA-1) is present as a mixture, where individual molecules may differ, for example, in terms of the distribution and length of polyester blocks.

[0039] The reaction conditions in the reaction according to step (i) are preferably selected such that the amide (PA-1) has a free amine functionality and a free OH functionality.

[0040] Preferably, the composition comprises an amide (PA-1) and further components such as catalysts or additives, for example waxes, stabilizers and fillers. The additives are typically present in the composition in amounts ranging up to 5%.

[0041] The reaction according to step (ii) is carried out under suitable conditions that allow the reaction of the diisocyanate with the free reactive groups of the amide (PA-1). According to the present invention, this reaction can be carried out in suitable equipment, where suitable processes are known per se to the person skilled in the art. It is also possible according to the present invention to use additives or auxiliaries to promote / improve the reaction according to step (i) or (ii). In particular, catalysts can be used.

[0042] Suitable catalysts for the reaction according to step (i) are known per se to the person skilled in the art. The catalyst may be used, for example, in an amount ranging from 10 to 200 ppm.

[0043] The reaction according to step (i), the reaction according to step (ii) or the reactions according to steps (i) and (ii) can in particular be carried out in an extruder.

[0044] The reaction in step (i) can be carried out, for example, at a temperature in the range of 200°C to 310°C, preferably in the range of 220°C to 300°C, particularly in the range of 220°C to 280°C, more preferably in the range of 230°C to 270°C, for a residence time of 10 seconds to 30 minutes, preferably 15 seconds to 10 minutes, for example, in a flowable softened or preferably molten state of the polyester and diamine, particularly by stirring, rolling, kneading, or preferably extrusion, for example using a conventional plasticizing apparatus, for example a mill, kneader or extruder, preferably an extruder.

[0045] The method according to the invention may comprise further steps, such as a temperature conditioning step or a shaping step.

[0046] Next, according to step (ii), the composition (Z1) is reacted with an isocyanate composition (I1) and a polyol composition (P1).

[0047] According to the invention, the polyol composition (P1) comprises at least one polyol, in particular at least one polycarbonate polyol (PC1).

[0048] Suitable polycarbonate polyols are known per se to those skilled in the art. In the context of the present invention, aliphatic polycarbonate diols are particularly suitable. Suitable polycarbonate diols include, for example, polycarbonate diols based on alkanediols. Suitable polycarbonate diols are strictly difunctional OH-functional polycarbonate diols, preferably strictly difunctional aliphatic OH-functional polycarbonate diols. Suitable polycarbonate diols are, for example, based on butanediol, pentanediol or hexanediol, in particular 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane-(1,5)-diol or mixtures thereof, particularly preferably 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or mixtures thereof. In the context of the present invention, preference is given to using polycarbonate diols based on butanediol and hexanediol, polycarbonate diols based on pentanediol and hexanediol, polycarbonate diols based on hexanediol, and mixtures of two or more of these polycarbonate diols.

[0049] In a further embodiment, the present invention also provides the thermoplastic polyurethane as described above, wherein the at least one polycarbonate polyol (PC1) is selected from the group consisting of polycarbonate diols based on butanediol and hexanediol, polycarbonate diols based on pentanediol and hexanediol, polycarbonate diols based on hexanediol, and mixtures of two or more of these polycarbonate diols.

[0050] The polycarbonate diol used preferably has a number average molecular weight Mn in the range of 500 to 4000 as determined by GPC, preferably in the range of 650 to 3500 as determined by GPC, more preferably in the range of 800 to 3000 as determined by GPC.

[0051] In a further embodiment, the present invention also provides the above thermoplastic polyurethane, wherein the at least one polycarbonate polyol (PC1) has a number average molecular weight Mn in the range of 500 to 4000, as determined by GPC.

[0052] According to the invention, the polyol composition (P1) may also comprise further polyols. Suitable polyols are known in principle to the person skilled in the art and are described, for example, in "Kunststoffhandbuch [Plastics Handbook], Volume 7, Polyurethane [Polyurethane]", Carl Hanser Verlag, 3rd Edition 1993, Chapter 3.1. Particularly preferably, polyesterols or polyetherols are used as polyols. Particularly preferably, polyetherpolyols are used. The number-average molecular weight of the polyols used according to the invention is preferably 500 g / mol to 3000 g / mol, preferably 600 g / mol to 2500 g / mol, in particular 650 g / mol to 2000 g / mol.

[0053] According to the invention, preferred polyetherols are polyethylene glycol, polypropylene glycol and polytetrahydrofuran.

[0054] According to the invention, the polyol composition can also comprise, for example, a solvent. Suitable solvents are known per se to the person skilled in the art.

[0055] In the context of the present invention, the reaction may also employ additives or adjuvants to the polyol composition, such as antioxidants, UV absorbers, UV filters, hydrolysis inhibitors, waxes, lubricants, plasticizers, processing aids, nucleating agents, fillers, and flame retardants.

[0056] According to the present invention, at least one isocyanate composition (I1) is used, which comprises at least one polyisocyanate. Preferably, the polyisocyanate used is a diisocyanate. According to the present invention, a mixture of two or more diisocyanates can also be used. In the context of the present invention, preferred diisocyanates are in particular aliphatic or aromatic diisocyanates.

[0057] Isocyanates which are preferably used include aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, more preferably tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI). ), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate, and / or 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and / or phenylene diisocyanate. Particularly preferably, 4,4'-MDI is used.

[0058] The aliphatic diisocyanates used are customary aliphatic and / or cycloaliphatic diisocyanates, such as, for example, tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, trimethylhexamethylene 1, 6-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4- and / or 2,6-diisocyanate, methylene dicyclohexyl 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI).

[0059] In a further embodiment, the present invention also provides the above thermoplastic polyurethane, wherein the polyisocyanate is selected from the group consisting of methylene diphenyl diisocyanate and aliphatic diisocyanates and diphenylmethane diisocyanate (MDI).

[0060] According to the present invention, the isocyanate composition can be used in pure form or in the form of a composition comprising a diisocyanate and at least one solvent. Suitable solvents are known to those skilled in the art. Suitable examples are non-reactive solvents such as ethyl acetate, methyl ethyl ketone, tetrahydrofuran and hydrocarbons.

[0061] According to the invention, further input materials, such as catalysts, or auxiliary and additive substances, can be added during the reaction according to step (ii).

[0062] Catalysts which particularly promote the reaction of NCO groups of isocyanate-reactive compounds with hydroxyl groups are, for example, tertiary amines, in particular triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane; in another preferred embodiment, they are organometallic compounds, for example titanates, iron compounds, preferably iron(III) acetylacetonate, tin compounds, preferably tin diacetate, tin dioctoate, tin dilaurate, or dialkyltin salts of aliphatic carboxylic acids, preferably dibutyltin diacetate, dibutyltin dilaurate, or bismuth salts, in which bismuth is preferably in the oxidation state 2 or 3, in particular 3. Salts of carboxylic acids are preferred. The carboxylic acids used are preferably carboxylic acids having 6 to 14 carbon atoms, particularly preferably having 8 to 12 carbon atoms. Examples of suitable bismuth salts include bismuth(III) neodecanoate, bismuth 2-ethylhexanoate, and bismuth octanoate.

[0063] The catalyst is preferably used in an amount of 0.0001 to 0.1 parts by weight based on 100 parts by weight of the isocyanate-reactive compound (b). Preferably, a tin catalyst, in particular tin dioctoate, is used.

[0064] The catalyst is generally used in an amount of 3 ppm to 2000 ppm, preferably 10 ppm to 1200 ppm, more preferably 20 ppm to 1000 ppm, and most preferably 30 ppm to 800 ppm.

[0065] In addition to the catalyst, the reaction according to step (ii) can also include conventional auxiliaries. Examples include surface-active substances, fillers, as well as flame retardants, nucleating agents, oxidation stabilizers, lubrication and demolding aids, dyes and pigments, and optionally stabilizers against, for example, hydrolysis, light, heat, discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers. Suitable auxiliaries and additives can be found, for example, in Kunststoffhandbuch, Vol. 7, Vieweg and Hoechtlen (eds.), Carl Hanser Verlag, Munich 1966 (pp. 103-113).

[0066] According to the present invention, a thermoplastic polyurethane is obtained. The properties of the thermoplastic polyurethane according to the present invention can vary within a wide range. Preferably, the thermoplastic polyurethane has a Shore hardness in the range of 45A to 78D, preferably in the range of 80A to 70D, particularly preferably in the range of 70A to 64D, more preferably in the range of 70A to 98A.

[0067] In a further embodiment, the present invention also provides the above thermoplastic polyurethane, wherein the thermoplastic polyurethane has a Shore hardness ranging from Shore 45A to Shore 78D.

[0068] In a further aspect, the present invention also provides a method for producing a thermoplastic polyurethane comprising the reaction of an isocyanate composition (I1) comprising at least one polyisocyanate with a polyol composition (P1), wherein a diamine (D1) having a molecular weight in the range of 50 g / mol to 700 g / mol is used.

[0069] Thus, the present invention also provides a method for producing a thermoplastic polyurethane comprising the reaction of an isocyanate composition (I1) comprising at least one polyisocyanate with a polyol composition (P1), in which at least one diamine (D1) having a molecular weight in the range of 50 g / mol to 700 g / mol is reacted with a thermoplastic polyester (PE-1) to obtain an amide (PA-1) prior to the reaction of the isocyanate composition (I1) with the polyol composition (P1).

[0070] In particular, the present invention relates to a process comprising steps (i) and (ii): (i) reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1); (ii) reacting the composition (Z1) obtained according to step (i) with an isocyanate composition (I1) comprising at least one polyisocyanate and with a polyol composition (P1); The present invention also relates to a method for producing a thermoplastic polyurethane comprising the steps of: Here, the diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol.

[0071] The present invention therefore further provides a method for producing a thermoplastic polyurethane comprising the reaction of an isocyanate composition (I1) comprising at least one polyisocyanate with a polyol composition (P1), the method comprising steps (i) and (ii): (i) reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1); (ii) reacting the composition (Z1) obtained according to step (i) with an isocyanate composition (I1) comprising at least one polyisocyanate and with a polyol composition (P1); Including, The diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol.

[0072] In an alternative embodiment, the present invention provides a composition comprising components (a)-(c): (a) an isocyanate composition (I1) comprising at least one polyisocyanate; (b) a polyol composition (P1), and (c) diamines (D1) as chain extenders, The present invention relates to a method for producing a thermoplastic polyurethane, comprising the steps of:

[0073] Regarding the preferred embodiment, reference is made to the above.

[0074] The present invention further provides a composition comprising the thermoplastic polyurethane according to the present invention.In the context of the present invention, the composition may comprise further components, such as fillers, glass fibers, plasticizers or flame retardants.The composition may comprise one or more of the above-mentioned components.

[0075] The invention further provides the use of the thermoplastic polyurethanes according to the invention described herein for the manufacture of coatings, damping elements, bellows, films or fibers, moldings, flooring for buildings and transport, nonwovens, preferably seals, wheels / rollers, shoe soles, hoses, cables, cable connectors, cable sheaths, cushions, laminates, profiles, belts, saddles, foams, plug connectors, trailing cables, solar cell modules, automotive trim. The use for the manufacture of cable sheaths is preferred. The manufacture is preferably carried out from pellet material by injection moulding, calendering, powder sintering or extrusion and / or by further foaming of the composition according to the invention.

[0076] In a further aspect, the present invention also provides a molded article comprising a thermoplastic polyurethane as described herein or obtainable or obtained by a process as described herein. The molded article according to the present invention may for example be a film, a molded article, a wheel / roller, a fiber, an automotive trim, a hose, a cable plug, a bellows, a trailing cable, a cable sheath, a seal, a belt or a damping element.

[0077] Due to the good mechanical and thermal properties, the thermoplastic polyurethanes according to the invention and the compositions according to the invention are particularly suitable for the production of films, moldings, wheels / rollers, fibers, automotive trims, hoses, cable plugs, bellows, trailing cables, cable sheaths, seals, belts or damping elements.

[0078] Thus, the present invention also provides a film, a molded article, a wheel / roller, a fiber, an automotive trim, a hose, a cable plug, a bellows, a trailing cable, a cable sheath, a seal, a belt or a damping element comprising the thermoplastic polyurethane described herein or the composition described herein.

[0079] In a further embodiment, the present invention also provides a molding as described herein, wherein the molding is selected from a film, a molding, a wheel / roller, a fiber, an automotive trim, a hose, a cable plug, a bellows, a trailing cable, a cable sheath, a seal, a belt, or a damping element.

[0080] Further embodiments of the invention can be found in the claims and the examples. It will be understood that the features of the subject matter / production method / use method according to the invention mentioned above and elucidated below can be used not only in the combinations specified in each case but also in other combinations without departing from the scope of the invention. Thus, for example, combinations of preferred features with particularly preferred features, or even non-featured features with particularly preferred features, etc., are also implicitly understood even if this combination is not explicitly mentioned.

[0081] Exemplary embodiments of the invention are described below, but are in no way intended to limit the invention. The invention particularly encompasses the embodiments resulting from the following references to the sub-relationships and therefore the combinations specified below.

[0082] 1. Thermoplastic polyurethanes obtainable or obtainable by a process comprising the reaction of an isocyanate composition (I1) comprising at least one polyisocyanate with a polyol composition (P1), At least one diamine (D1) having a molecular weight in the range of 50 g / mol to 700 g / mol is used.

[0083] 2. The thermoplastic polyurethane according to embodiment 1, wherein the diamine D1 is reacted with a thermoplastic polyester (PE-1) to give an amide (PA-1) prior to the reaction of the isocyanate composition (I1) with the polyol composition (P1).

[0084] 3. The method comprises steps (i) and (ii): (i) reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1); (ii) reacting the composition (Z1) obtained according to step (i) with an isocyanate composition (I1) comprising at least one polyisocyanate and with a polyol composition (P1); Including, 3. The thermoplastic polyurethane according to embodiment 1 or 2, wherein the diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol.

[0085] 4. The thermoplastic polyurethane according to embodiment 1, wherein the diamine (D1) is used as a chain extender.

[0086] 5. The method comprises the steps of: (a) the isocyanate composition (I1) containing at least one polyisocyanate, (b) the polyol composition (P1), and (c) the diamine (D1) as chain extender, 5. The thermoplastic polyurethane of embodiment 4, comprising the reaction of:

[0087] 6. The diamine (D1) is selected from compounds of general formula (I) or (II): [ka] wherein R1 and R2 are independently selected from the group consisting of O-CH3, CH2CH3, S-CH3, NH-CH3, N(CH3)2 and H, or [ka] (In the formula, a) X1 = X2 = Y1 = Y2 = H, b) X1 = X2 = Y1 = Y2 = CH3; c) X1 = X2 = Y1 = Y2 = isopropyl; d) X1 = X2 = Y1 = Y2 = C2H5; e) X1 = X2 = Y1 = Y2 = butyl; f) X1 = X2 = Y1 = Y2 = tert-butyl; g) X1=X2=H and Y1=Y2=CH3, h) X1=X2=H, and Y1=Y2=isopropyl; i) X1=X2=H and Y1=Y2=C2H5; j) X1=X2=H and Y1=Y2=butyl, or k) X1=X2=H, and Y1=Y2=tert-butyl; Z is selected from the group consisting of CH2, CHCH3, C(CH3)2, O, and S. The thermoplastic polyurethane of any one of embodiments 1 to 5.

[0088] 7. The diamine (D1) has the general formula (III): [ka] wherein R1=R2=S-CH3 or R1=R2=CH2CH3. The thermoplastic polyurethane of any one of the preceding embodiments.

[0089] 8. The thermoplastic polyurethane according to any one of the preceding claims, wherein the polyol composition (P1) comprises at least one polycarbonate polyol (PC1).

[0090] 9. The thermoplastic polyurethane according to any one of the preceding claims, wherein the thermoplastic polyester (PE-1) has a molecular weight in the range of 1500 g / mol to 60000 g / mol.

[0091] 10. The thermoplastic polyurethane of any one of the preceding claims, wherein the thermoplastic polyester (PE-1) is selected from the group consisting of polyalkylene terephthalates and poly-L-lactic acid.

[0092] 11. The thermoplastic polyurethane according to any one of the preceding claims, wherein the polyester (PE-1) has a molecular weight in the range of 1000 g / mol to 5000 g / mol.

[0093] 12. The thermoplastic polyurethane of any one of the preceding claims, wherein the polyisocyanate is selected from the group consisting of methylene diphenyl diisocyanate and aliphatic diisocyanates.

[0094] 13. The thermoplastic polyurethane of any one of the preceding claims, having a Shore hardness ranging from Shore 45A to Shore 78D.

[0095] 14. A method for producing a thermoplastic polyurethane, comprising reacting an isocyanate composition (I1) containing at least one polyisocyanate with a polyol composition (P1), in which at least one diamine (D1) having a molecular weight in the range of 50 g / mol to 700 g / mol is used.

[0096] 15. Steps (i) and (ii): (i) reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1); (ii) reacting the composition (Z1) obtained according to step (i) with an isocyanate composition (I1) comprising at least one polyisocyanate and with a polyol composition (P1); Including, 15. The method for producing a thermoplastic polyurethane according to embodiment 14, wherein the diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol.

[0097] 16.Ingredients (a)~(c): (a) the isocyanate composition (I1) containing at least one polyisocyanate, (b) the polyol composition (P1), and (c) the diamine (D1) as chain extender, 15. A method for producing the thermoplastic polyurethane of embodiment 14, comprising reacting

[0098] 17. The method according to any one of embodiments 14 to 16, wherein the diamine (D1) is used as a chain extender.

[0099] 18. The diamine (D1) is selected from compounds of general formula (I) or (II): [ka] wherein R1 and R2 are independently selected from the group consisting of O-CH3, CH2CH3, S-CH3, NH-CH3, N(CH3)2 and H, or [ka] (In the formula, a) X1 = X2 = Y1 = Y2 = H, b) X1 = X2 = Y1 = Y2 = CH3; c) X1 = X2 = Y1 = Y2 = isopropyl; d) X1 = X2 = Y1 = Y2 = C2H5; e) X1 = X2 = Y1 = Y2 = butyl; f) X1 = X2 = Y1 = Y2 = tert-butyl; g) X1=X2=H and Y1=Y2=CH3, h) X1=X2=H, and Y1=Y2=isopropyl; i) X1=X2=H and Y1=Y2=C2H5; j) X1=X2=H and Y1=Y2=butyl, or k) X1=X2=H, and Y1=Y2=tert-butyl; The method of any one of embodiments 14 to 17, wherein Z is selected from the group consisting of CH2, CHCH3, C(CH3)2, O and S.

[0100] 19. The diamine (D1) has the general formula (III): [ka] (wherein R1=R2=S-CH3 or R1=R2=CH2CH3),

[0101] 20. The method according to any one of embodiments 14 to 19, wherein the polyol composition (P1) comprises at least one polycarbonate polyol (PC1).

[0102] 21. The method according to any one of embodiments 14 to 20, wherein the thermoplastic polyester (PE-1) has a molecular weight in the range of 1500 g / mol to 60000 g / mol.

[0103] 22. The method according to any one of embodiments 14 to 21, wherein the thermoplastic polyester (PE-1) is selected from the group consisting of polyalkylene terephthalates and poly-L-lactic acid.

[0104] 23. The method according to any one of embodiments 14 to 22, wherein the polyester (PE-1) has a molecular weight in the range of 1000 g / mol to 5000 g / mol.

[0105] 24. The method of any one of embodiments 14 to 23, wherein the polyisocyanate is selected from the group consisting of methylene diphenyl diisocyanate and aliphatic diisocyanates.

[0106] 25. The method of any one of embodiments 14 to 24, wherein the thermoplastic polyurethane has a Shore hardness ranging from Shore 45A to Shore 78D.

[0107] 26. A molding comprising a thermoplastic polyurethane according to any one of embodiments 1 to 13, or a thermoplastic polyurethane obtainable or obtainable by the method according to any one of embodiments 14 to 25.

[0108] 27. The molding of embodiment 26, selected from a film, a molding, a wheel / roller, a fiber, an automotive trim, a hose, a cable plug, a bellows, a trailing cable, a cable sheath, a seal, a belt, or a damping element.

[0109] 28. Steps (i) and (ii): (i) reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1); (ii) reacting the composition (Z1) obtained according to step (i) with an isocyanate composition (I1) comprising at least one polyisocyanate and with a polyol composition (P1); A thermoplastic polyurethane obtainable or obtained by a process comprising The diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol and has the general formula (III): [ka] (wherein R1=R2=S-CH3 or R1=R2=CH2CH3), thermoplastic polyurethanes.

[0110] 29. The thermoplastic polyurethane according to embodiment 28, wherein the polyol composition (P1) comprises at least one polycarbonate polyol (PC1).

[0111] 30. The thermoplastic polyurethane according to embodiment 28 or 29, wherein the thermoplastic polyester (PE-1) has a molecular weight in the range of 1500 g / mol to 60000 g / mol.

[0112] 31. The thermoplastic polyurethane according to any one of embodiments 28 to 30, wherein the thermoplastic polyester (PE-1) is selected from the group consisting of polyalkylene terephthalates and poly-L-lactic acid.

[0113] 32. The thermoplastic polyurethane according to any one of embodiments 28 to 31, wherein the polyester (PE-1) has a molecular weight in the range of 1000 g / mol to 5000 g / mol.

[0114] 33. The thermoplastic polyurethane of any one of embodiments 28 to 32, wherein the polyisocyanate is selected from the group consisting of methylene diphenyl diisocyanate and aliphatic diisocyanates.

[0115] 34. The thermoplastic polyurethane of any one of embodiments 28 to 33, having a Shore hardness ranging from Shore 45A to Shore 78D.

[0116] 35. Steps (i) and (ii): (i) reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1); (ii) reacting the composition (Z1) obtained according to step (i) with an isocyanate composition (I1) comprising at least one polyisocyanate and with a polyol composition (P1); A method for producing a thermoplastic polyurethane comprising: The diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol and has the general formula (III): [ka] (wherein R1=R2=S-CH3 or R1=R2=CH2CH3), the method.

[0117] 36. A molding comprising a thermoplastic polyurethane according to any one of embodiments 28 to 34, or a thermoplastic polyurethane obtainable or obtainable by the method according to embodiment 35.

[0118] 37. The molding of embodiment 36, selected from a film, a molding, a wheel / roller, a fiber, an automotive trim, a hose, a cable plug, a bellows, a trailing cable, a cable sheath, a seal, a belt, or a damping element.

[0119] 38. Thermoplastic polyurethanes obtainable or obtained by a process comprising the reaction of an isocyanate composition (I1) comprising at least one polyisocyanate with a polyol composition (P1), A thermoplastic polyurethane, comprising at least one diamine (D1) having a molecular weight in the range of 50 g / mol to 700 g / mol reacted with a thermoplastic polyester (PE-1) to obtain an amide (PA-1) prior to the reaction of said isocyanate composition (I1) with said polyol composition (P1).

[0120] 39. The method, comprising steps (i) and (ii): (i) reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1); (ii) reacting the composition (Z1) obtained according to step (i) with an isocyanate composition (I1) comprising at least one polyisocyanate and with a polyol composition (P1); Including, The thermoplastic polyurethane according to embodiment 38, wherein the diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol.

[0121] 40. The diamine (D1) is selected from compounds of general formula (I) or (II): [ka] wherein R1 and R2 are independently selected from the group consisting of O-CH3, CH2CH3, S-CH3, NH-CH3, N(CH3)2 and H, or [ka] (In the formula, a) X1 = X2 = Y1 = Y2 = H, b) X1 = X2 = Y1 = Y2 = CH3; c) X1 = X2 = Y1 = Y2 = isopropyl; d) X1 = X2 = Y1 = Y2 = C2H5; e) X1 = X2 = Y1 = Y2 = butyl; f) X1 = X2 = Y1 = Y2 = tert-butyl; g) X1=X2=H and Y1=Y2=CH3, h) X1=X2=H, and Y1=Y2=isopropyl; i) X1=X2=H and Y1=Y2=C2H5; j) X1=X2=H and Y1=Y2=butyl, or k) X1=X2=H, and Y1=Y2=tert-butyl; Z is selected from the group consisting of CH2, CHCH3, C(CH3)2, O, and S. The thermoplastic polyurethane of any one of embodiments 38 and 39.

[0122] 41. The diamine (D1) has the general formula (III): [ka] The thermoplastic polyurethane of any one of embodiments 38 to 40, wherein R1=R2=S-CH3 or R1=R2=CH2CH3.

[0123] 42. The thermoplastic polyurethane according to any one of embodiments 38 to 41, wherein the polyol composition (P1) comprises at least one polycarbonate polyol (PC1).

[0124] 43. The thermoplastic polyurethane according to any one of embodiments 38 to 42, wherein the thermoplastic polyester (PE-1) has a molecular weight in the range of 1500 g / mol to 60000 g / mol.

[0125] 44. The thermoplastic polyurethane of any one of embodiments 38 to 43, wherein the thermoplastic polyester (PE-1) is selected from the group consisting of polyalkylene terephthalates and poly-L-lactic acid.

[0126] 45. The thermoplastic polyurethane according to any one of embodiments 38 to 44, wherein the polyester (PE-1) has a molecular weight in the range of 1000 g / mol to 5000 g / mol.

[0127] 46. ​​The thermoplastic polyurethane of any one of embodiments 38 to 45, wherein the polyisocyanate is selected from the group consisting of methylene diphenyl diisocyanate and aliphatic diisocyanates.

[0128] 47. The thermoplastic polyurethane of any one of embodiments 38 to 46, having a Shore hardness ranging from Shore 45A to Shore 78D.

[0129] 48. A method for producing a thermoplastic polyurethane, comprising reacting an isocyanate composition (I1) containing at least one polyisocyanate with a polyol composition (P1), A method for producing a thermoplastic polyurethane, comprising reacting at least one diamine (D1) having a molecular weight in the range of 50 g / mol to 700 g / mol with a thermoplastic polyester (PE-1) to obtain an amide (PA-1) prior to the reaction of the isocyanate composition (I1) with the polyol composition (P1).

[0130] 49. Steps (i) and (ii): (i) reacting a thermoplastic polyester (PE-1) with a diamine (D1) to obtain a composition (Z1) comprising an amide (PA-1); (ii) reacting the composition (Z1) obtained according to step (i) with an isocyanate composition (I1) comprising at least one polyisocyanate and with a polyol composition (P1); Including, 49. A method for producing a thermoplastic polyurethane comprising reacting an isocyanate composition (I1) comprising at least one polyisocyanate according to embodiment 48, wherein the diamine (D1) has a molecular weight in the range of 50 g / mol to 700 g / mol, with a polyol composition (P1).

[0131] 50. A molding comprising a thermoplastic polyurethane according to any one of embodiments 38 to 47, or a thermoplastic polyurethane obtainable or obtainable by the method according to embodiment 48 or 49.

[0132] 51. The molding of embodiment 50, selected from a film, a molding, a wheel / roller, a fiber, an automotive trim, a hose, a cable plug, a bellows, a trailing cable, a cable sheath, a seal, a belt, or a damping element.

[0133] The following examples serve to illustrate the invention but are in no way limiting with respect to the subject matter thereof. EXAMPLES

[0134] 1. Input materials PC polyol: Polycarbonate polyol E1195A: Standard TPU (Benchmark), Elastollan 1195 A, a polyurethane based on thermoplastic polyether, available from BASF Polyurethanes 785A HPM: Standard HPM TPU (Benchmark), Elastollan 785 A HPM, a polyurethane based on thermoplastic polyether, available from BASF Polyurethanes Ethacure 300: Dimethylthiotoluenediamine (E300) Ethacure 100: Diethyltoluenediamine (E100).

[0135] 2. Typical manufacturing examples 2.1 The synthesis was carried out by reactive extrusion using a self-cleaning twin screw extruder according to the method described in EP1419188B1. The twin screw extruder with a screw length to screw diameter ratio of 48 achieved a residence time of at least 40 seconds, preferably more than 60 seconds. The polymer melt obtained after the transamidation reaction and subsequent chain synthesis was processed into pellet material by underwater or strand pelletization.

[0136] 2.2 Mechanical properties of various samples were investigated. Compositions containing thermoplastic polyurethane and dimethylthiotoluenediamine / diethylthiotoluenediamine were prepared by one-shot process or by prepolymer process.

[0137] The one-shot process involved using all the ingredients (diisocyanate (a), polyol (b), chain extender (c) and catalyst (e)) in the first zone of the extruder. The temperature was adjusted to a range of 150°C to 230°C at 200 rpm. After mixing the ingredients and reacting for at least 40 seconds, preferably at least 60 seconds, the pellet material was obtained from the polymer melt by strand pelletization or underwater pelletization.

[0138] The semi-prepolymer process involved first using diisocyanate (a), polyol (b), chain extender (c) and catalyst (e) in the first zone of the extruder. These inputs were mixed and pre-reacted, and then additional chain extender was added in the third or fifth zone. After reaction for at least 40 seconds, preferably at least 60 seconds, pelletized material was obtained from the polymer melt by strand pelletizing or underwater pelletizing.

[0139] 2.3 Conditions for Aging The SI test specimens were stored in a convection oven at the appropriate temperature for a given time. After heat treatment, they were removed and cooled to room temperature. The thus treated specimens were subjected to mechanical testing.

[0140] The ageing tests show that the thermoplastic polyurethanes according to the invention, with different hard segment percentages and produced using dimethylthiotoluenediamine or diethyltoluenediamine, were dimensionally stable after storage at 180°C, 190°C and 200°C for 6 hours and also retained the flexibility of the material. Moreover, even after storage at 150°C for 3000 hours, they retained more than 50% of their original elongation at break. Thus, the material meets the requirements of the T4 standard for applications in the automotive sector.

[0141] 3. Working Example 3.1 The examples identified below were produced on a Coperion ZSK58 MC twin screw extruder with a processing length of 48 D (12 barrels). A gear pump discharged the melt from the extruder. After filtration, the polymer melt was processed by underwater pelletization and continuously dried in a heated fluidized bed at 60-90° C. to a moisture content of less than 0.03%.

[0142] Polybutylene terephthalate Ultradur B4500 from BASF SE was metered into the first zone. Once the PBT was melted, reagents for the transamidation reaction, e.g. Etacure 100, and optionally a catalyst, were fed into the third zone. Once the transamidation reaction was complete, further reaction components such as diisocyanates and polyols were added in the fifth zone. Further additives were added in the eighth zone. Discharge and underwater pelletization of the melt took place at a melt temperature of 220-230°C.

[0143] The barrel temperature in zone 1, the feed section, was 150°C. Melting and transesterification reactions in zones 2-5 were carried out at temperatures of 250-300°C. Polymer synthesis in zones 6-12 was carried out at barrel temperatures of 240-210°C. The screw speed was 180-240 rpm. Throughput was in the range of 180-220 kg / h.

[0144] 3.2 Composition Example 1: E1195A with BDO Example 2: Polycarbonate polyol HPM TPU+E100, (97A) Example 3: 785A HPM TPU with BDO Example 4: Polycarbonate polyol HPM TPU+E100, (92A) Example 5: Aliphatic HPM with E100, (86A) Example 6: Polycarbonate Polyol Aromatic TPU+E300.

[0145] 4.Results 4.1 Overview of ageing characteristics for cable applications (Class D)

[0146] [Table 1]

[0147] 4.2 Summary of ageing characteristics for cable applications (Class E, 240°C, 6 hours)

[0148] [Table 2]

[0149] 5. Results after storage 5.1 Storage at 150℃ for 3000 hours

[0150] [Table 3]

[0151] 5.2 Storage at 175°C and 85% RH for 10 days

[0152] [Table 4]

[0153] 5.3 Storage at 200℃ for 6 hours

[0154] [Table 5]

[0155] 5.4 Storage at 85℃ and 85% RH for 3000 hours

[0156] [Table 6]

[0157] 6. The following properties of the obtained polyurethane were determined by the methods specified below: Shore hardness: DIN ISO 7619-1 Tensile strength and elongation at break: DIN 53504 Tear resistance: DIN ISO 34-1,B(b) Abrasion measurements: DIN ISO 4649 Density: DIN EN ISO 1183-1, A Compression set: DIN ISO 815.

[0158] References Kunststoffhandbuch, Volume 7, edited by Vieweg and Hoechtlen, Carl Hanser Verlag, Munich 1966 (pp. 103-113) EP 1 419 188 B1

Claims

1. A process comprising the steps of: (i) reacting a thermoplastic polyester (PE-1) with at least one diamine (D1) having a molecular weight in the range of 50 g / mol to 700 g / mol to obtain a composition (Z1) comprising an amide (PA-1); (ii) reacting the composition (Z1) obtained according to step (i) with an isocyanate composition (I1) containing at least one polyisocyanate and a polyol composition (P1); Including, A method for producing thermoplastic polyurethane.

2. The diamine (D1) is selected from compounds of general formula (I) or (II): 【Chemistry 1】 (Wherein, R1 and R2 are independently O—CH ３ , C.H. ２ CH ３ , S-CH ３ , NH-CH ３ , N(CH ３ ) ２ and H), or 【Chemistry 2】 (In the formula, a)X １ =X ２ =Y １ =Y ２ =H、 b)X １ =X ２ =Y １ =Y ２ =CH ３ 、 c) X １ =X ２ = Y １ = Y ２ = isopropyl, d)X １ =X ２ =Y １ =Y ２ =C ２ H ５ 、 e) X １ =X ２ = Y １ = Y ２ = butyl, f) X １ =X ２ = Y １ = Y ２ = tert-butyl, g) X １ = X ２ = H, and Y １ = Y ２ = CH ３ , h) X １ =X ２ = H and Y １ = Y ２ = isopropyl, i) X １ = X ２ = H, and Y １ = Y ２ = C ２ H ５ , j) X １ =X ２ = H and Y １ = Y ２ = butyl, or k) X １ =X ２ = H and Y １ = Y ２ = tert-butyl, Z is CH ２ , CHCH ３ , C(CH ３ ) ２ , O and S), A method for producing the thermoplastic polyurethane according to claim 1.

3. The diamine (D1) has the general formula (III): 【Chemistry 3】 (In the formula, R1=R2=S-CH ３ Or R1 = R2 = CH ２ CH ３ The method for producing the thermoplastic polyurethane according to claim 1 or 2,

4. 4. A process for producing a thermoplastic polyurethane according to claim 1, wherein the polyol composition (P1) comprises at least one polycarbonate polyol (PC1).

5. The method for producing a thermoplastic polyurethane according to any one of claims 1 to 4, wherein the thermoplastic polyester (PE-1) has a molecular weight in the range of 1500 g / mol to 60000 g / mol.

6. The method for producing a thermoplastic polyurethane according to any one of claims 1 to 5, wherein the thermoplastic polyester (PE-1) is selected from the group consisting of polyalkylene terephthalate and poly-L-lactic acid.

7. The method for producing a thermoplastic polyurethane according to any one of claims 1 to 6, wherein the polyester (PE-1) has a molecular weight in the range of 1000 g / mol to 5000 g / mol.

8. 8. The method for producing a thermoplastic polyurethane according to any one of claims 1 to 7, wherein the polyisocyanate is selected from the group consisting of methylene diphenyl diisocyanate and aliphatic diisocyanates.

9. A method for producing a thermoplastic polyurethane according to any one of claims 1 to 8, wherein the thermoplastic polyurethane has a Shore hardness in the range of Shore 45A to Shore 78D.

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