TPU FOR INMOLD ASSEMBLY OF AN OUTER SHOE SOLE ON ETPU

Abstract

A molded article (M) contains a molded article (M-1) made of a thermoplastic elastomer (TPE-1) and a foamed pellet material made of a thermoplastic elastomer (TPE-2). The molded article (M-1) has a softening temperature TS (TPE-1) that deviates by no more than 25° C. from the processing temperature TP (TPE-2) of the thermoplastic elastomer (TPE-2). The softening temperature is determined by TMA in accordance with ISO 11359-3:2014. A process can be used for producing the molded article. The molded article can be used for application in the sports, industry, medicine, sports medicine, safety, automotive and consumer goods field, especially as a shoe sole, a part of a shoe sole, a bicycle saddle, a cushioning, a mattress, an underlay, a grip, a protective film, or a component in automobile interiors and exteriors.

Claims

1-17. (canceled)

18: A molded article (M), comprising: a molded article (M-1) made of a thermoplastic elastomer (TPE-1), and a foamed pellet material made of a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS (TPE-1) that deviates by no more than 25° C. from a processing temperature range TP (TPE-2) of the thermoplastic elastomer (TPE-2), the softening temperature TS (TPE-1) being determined by thermomechanical analysis (TMA) in accordance with ISO 11359-3:2014, wherein the processing temperature range TP (TPE-2) is a range from 100 to 170° C., wherein the thermoplastic elastomer (TPE-1) is in compact form, and wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are each independently selected from the group consisting of a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, and a polyesterester.

19: The molded article according to claim 18, wherein the thermoplastic elastomer (TPE-1) has a maximum softening of less than 10% at a temperature below the processing temperature range TP (TPE-2), and in the processing temperature range TP (TPE-2) has a softening in a range from 3% to 12%, the softening being determined by TMA in accordance with ISO 11359-3:2014.

20: The molded article according to claim 18, wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are each independently selected from the group consisting of a thermoplastic polyurethane, a thermoplastic polyester, and a thermoplastic polyamide.

21: The molded article according to claim 18, wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are each independently a thermoplastic polyurethane.

22: The molded article according to claim 18, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane (TPU-1) obtained by reaction of the components (i) to (iii): (i) a polyisocyanate composition (IC); (ii) at least one chain extender (CE1), and (iii) a polyol composition (PC), wherein the components (i) to (iii) are reacted at an index in a range from 0.99 to 1.02, and wherein an average molecular weight of polyols present in the polyol composition (PC) is in a range from 1250 g/mol to 2500 g/mol.

23: The molded article according to claim 22, wherein the at least one chain extender (CE1) is at least one selected from the group consisting of ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol, and hexane-1,6-diol.

24: The molded article according to claim 22, wherein the polyol composition (PC) comprises at least one polyol selected from the group consisting of a polyetherol, a polyesterol, and a polycaprolactone polyol.

25: The molded article according to claim 22, wherein the polyol composition (PC) comprises at least one polytetrahydrofuran having a number-average molecular weight Mn in a range from 1400 g/mol to 2200 g/mol.

26: A process for producing a molded article (M), comprising: (a) providing a molded article (M-1), comprising a thermoplastic elastomer (TPE-1), in a mold, (b) filling the mold with a foamed pellet material comprising a thermoplastic elastomer (TPE-2), the thermoplastic elastomer (TPE-2) having a processing temperature range TP (TPE-2), and (c) producing the molded article (M) by welding at a temperature in a range from 100 to 170° C., wherein the molded article (M-1) has a softening temperature TS (TPE-1) that deviates by no more than 25° C. from the processing temperature range TP (TPE-2), the softening temperature TS (TPE-1) being determined by thermomechanical analysis (TMA) in accordance with ISO 11359-3:2014, and the processing temperature range TP (TPE-2) being a range from 100 to 170° C., wherein the thermoplastic elastomer (TPE-1) is in compact form, and wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are each independently selected from the group consisting of a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, and a polyesterester.

27: The process according to claim 26, wherein the thermoplastic elastomer (TPE-1) has a maximum softening of less than 10% at a temperature below the processing temperature range TP (TPE-2), and in the processing temperature range TP (TPE-2) has a softening in a range from 3% to 12%, the softening being determined by TMA in accordance with ISO 11359-3:2014.

28: The process according to claim 26, wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are each independently a thermoplastic polyurethane.

29: A molded article, obtained by the process according to claim 26.

30: A method, comprising: producing a molded article (M) with a molded article (M-1) in the presence of a foamed pellet material made of a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS (TPE-1) that deviates by no more than 25° C. from a processing temperature range TP (TPE-2) of the thermoplastic elastomer (TPE-2), the softening temperature being determined by thermomechanical analysis (TMA) in accordance with ISO 11359-3:2014, wherein the processing temperature range TP (TPE-2) is a range from 100 to 170° C., wherein the thermoplastic elastomer (TPE-1) is in compact form, and wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are each independently selected from the group consisting of a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, and a polyesterester.

31: The method according to claim 30, wherein the thermoplastic elastomer (TPE-1) has a maximum softening of less than 10% at a temperature below the processing temperature range TP (TPE-2), and in the processing temperature range TP (TPE-2) has a softening in a range from 3% to 12%, the softening being determined by TMA in accordance with ISO 11359-3:2014.

32: The method according to claim 30, wherein the molded article (M) is suitable for application in the sports, industry, medicine, sports medicine, safety, automotive, and/or consumer goods field.

33: The method according to claim 30, wherein the molded article (M) is part of a shoe sole, a bicycle saddle, cushioning, a mattress, an underlay, a grip, a protective film, or a component in automobile interiors and exteriors.

34: The method according to claim 30, wherein the molded article (M) is a shoe outer sole.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0162] FIG. 1: shows the results of the TMA measurements (heating rate 20 K/min). The depth in % (y axis) is plotted against the temperature in ° C. (x axis). Shown are examples 1, 2, 4. 5 and 6 and also comparative examples 1 to 4. Measurements were performed directly on the non-heat-treated outer soles. Only in the case of comparative examples 1 and 2 was the sole heat treated at 70° C. for 10 h prior to the TMA measurement.

[0163] The examples that follow serve to illustrate the invention but are in no way limiting with regard to the subject matter of the present invention.

EXAMPLES

1. Starting Materials

[0164] The following starting materials were used: [0165] Polyol 1: polyether polyol having a number-average molar mass of 1 kg/mol and exclusively primary OH groups (based on tetramethylene oxide, functionality: 2) [0166] Polyol 2: polyether polyol having a number-average molar mass of 2 kg/mol and exclusively primary OH groups (based on tetramethylene oxide, functionality: 2) [0167] Isocyanate 1: aromatic isocyanate (4,4′-methylenediphenyl diisocyanate) [0168] CE 1: butane-1,4-diol [0169] Plasticizer 1: acetyl tributyl citrate, abbreviated to ATBC, also referred to hereinafter as P1 [0170] Catalyst 1: tin(II) isooctoate (50% in dioctyl adipate) [0171] Stabilizer 1: sterically hindered phenol [0172] Processing [0173] auxiliary 1: ethylenebisstearoylamide, hereinafter also referred to as PA1 [0174] Crosslinker 1: TPU 1, which in a separate extrusion step was reacted with 40% of a 2.4 functional prepolymer based on 4,4′-methylenediphenyl diisocyanate (MDI), polymeric MDI and a polyether polyol having a number-average molar mass of 0.5 kg/mol and exclusively primary OH groups (based on tetramethylene oxide, functionality: 2), the residual NCO of which is 28.5 g/100 g (ASTM D 5155-96).

1.1 Preparation of TPU 1

[0175] A mixture of 5.72 percent by mass of butane-1,4-diol and 62.72 percent by mass of polytetrahydrofuran having a number-average molar mass Mn of 1000 g/mol was heated to 70° C. and mixed in a mixing head intensively with 31.56 percent by mass of diphenylmethane 4,4′-diisocyanate in the presence of 1.0 percent by mass of Crodamide EBS wax based on the first three components. The reaction mixture obtained was applied to a circulating PTFE belt at a temperature of 90° C. The reaction mixture that had solidified to form a solid slab at the end of the belt was fed continuously at about 80° C. via intake rolls directly to a comminution and homogenization apparatus. It was comminuted therein at temperatures of about 105° C. and conveyed to a single-shaft extruder connected thereto by a tangential flange. The barrel temperatures were about 17° C. to 19° C. in the intake region, and 190 to 220° C. in the middle zone. The melt that exited at the die plate was processed by means of underwater pelletization to give homogeneous lenticular pellets having a mass of 32 mg and then dried.

1.2 Preparation of the eTPU

[0176] In an impregnation vessel with a degree of filling of 80%, the TPU 1 pellets were added to a mixture of water with calcium carbonate and a surface-active substance such that the solid/liquid phase ratio was 0.32. The gas-tight vessel was first purged with nitrogen before the blowing agent butane was injected in the amounts indicated in the table, based on the solid phase (TPU). The vessel was heated while stirring the solid/liquid phase, and at a temperature of 50° C. the vessel was pressurized with a defined amount of nitrogen to a pressure of 8 bar. The mixture was then further heated up to the desired impregnation temperature (IMT). On reaching the impregnation temperature and impregnation pressure, the pressure in the vessel was released via a valve after a specified hold time. The precise production parameters for the experiments and the bulk densities achieved are listed in the following table 1.

TABLE-US-00001 TABLE 1 Blowing agent concentration Hold time based on amount (range IMT −5° C. of solid phase to IMT +2° C.) IMT Bulk density Name (% by wt.) (min) (° C.) (g/L) eTPU 1 30 9 120 106

2. Production of Comparative Examples+Examples (Compact TPU)

2.1 Production Process 1—(2-Stage Process Comprising First Step, Reactive Extrusion Process without Plasticizer, with Polyol Mixture, and Second Step, Incorporation of P1 on Twin-Screw Extruder), Process for Continuous Synthesis of Comparative Example 1

[0177] A mixture of CE1, processing auxiliary 1, stabilizer 1, polyol 1 and polyol 2, on the one hand, was metered at a charge temperature of 150° C. into the first barrel of a ZSK 92 twin-screw extruder from Werner & Pfleiderer, Stuttgart, having a processing length of 56 D and, separately from this, isocyanate 1 was metered at a charge temperature of 65° C. into the first barrel of this same extruder. The speed of the twin screw was 280 rpm. The set temperature values for the barrels in the downstream direction were 190° C. in the first third of the screw and 190° C. in the second and third thirds of the screw. The output was 850 kg/h. In this way, the thermoplastic polyurethane (TPU) is synthesized in the known reaction extruder process. The pelletizable reaction melt thus obtained can be formed into lenticular pellets in the subsequent process—what is known as underwater pelletization. The pellets are dried by subsequent aftertreatment at approximately 80 to 90° C. and they are thereafter packaged in transportable containers. The preliminary product 1 obtained from this is processed further as described below.

[0178] Preliminary product 1 is metered at a charge temperature of approximately 30° C. into the first barrel of a ZE 65 twin-screw extruder from Berstorff, having a processing length of 42 D. Separately from this, plasticizer 1 is metered at a charge temperature of 40° C. into the fourth barrel of this same extruder. The speed of the twin screw is 160 rpm. The set temperature values for the barrels in the downstream direction are 190° C. in the first third of the screw and 170° C. in the second and third thirds of the screw. The output is 300 kg/h. In this way, the thermoplastic polyurethane (TPU) is synthesized in the known compounding process. The pelletizable polymer melt thus obtained can be formed into lenticular pellets in the subsequent process—what is known as underwater pelletization. The pellets are dried by subsequent aftertreatment at approximately 80° C. and they are thereafter packaged in transportable containers, in this case 25 kg PE bags.

[0179] The TPU pellets thus obtained are pre-dried at 80 to 100° C. for 3 h prior to further processing, and then formed into test specimens by injection molding. The zone temperatures of the injection molding units used for this purpose are between 190° C. and 220° C. S2 test bars are stamped out from the specimen panels thus obtained and are subjected to further mechanical tests. In addition, the chemical values, such as for example molar mass, of these test specimens are determined.

2.2 Production Process 2—Dry Blend, i.e. Mixing of TPU Pellets with Crosslinker 1, Process for Continuous Synthesis of Comparative Example 2

[0180] 98.5 parts by weight of TPU pellets produced as under 2.1 are pre-dried at 80 to 100° C. for 3 h for further processing and subsequently mixed with 1.5 parts by weight of crosslinker 1.

[0181] The TPU pellet mixture thus obtained is formed into test specimens by injection molding. The zone temperatures of the injection molding units used for this purpose are between 190° C. and 220° C. S2 test bars are stamped out from the specimen panels thus obtained and are subjected to further mechanical tests. In addition, the chemical values, such as for example molar mass, of these test specimens are determined.

[0182] The synthesis and properties of the thermoplastic polyurethanes obtained are summarized in tables 2 and 3. The samples produced using these processes serve as comparative examples 1+2.

TABLE-US-00002 TABLE 2 Synthesis of comparative examples 1 + 2: Preliminary Comparative Comparative product 1 example 1 example 2 Polyol 1 [g] 500 Polyol 2 [g] 500 Isocyanate 1 [g] 372 CE 1 [g] 65 Stabilizer 1 [g] 14.5 Preliminary product 1 [g] 850 Plasticizer 1 [g] 150 Processing auxiliary 1 [g] <1 Comparative example 1 [g] 985 Crosslinker 1 [g] 15 Index 1010 — —

TABLE-US-00003 TABLE 3 Properties of comparative examples 1 + 2: Comparative Comparative example 1 example 2 Shore A 62 63 Tensile strength [MPa] 26 27 Elongation at break [%] 975 890 Tear propagation resistance 41 45 [kN/m] Abrasion [mm.sup.3] 60 53 GPC molar mass [10.sup.3 daltons] 125 260

2.3 Production Process 3—(Single-Stage Reactive Extrusion Process with P1+Polyol Mixture), Process for Continuous Synthesis of Comparative Example 3 and Example 3

[0183] A mixture of CE1, processing auxiliary 1, stabilizer 1, polyol 1 and polyol 2, on the one hand, was metered at a charge temperature of 150° C. into the first barrel of a ZSK 92 twin-screw extruder from Werner & Pfleiderer, Stuttgart, having a processing length of 56 D and, separately from this, isocyanate 1 was metered at a charge temperature of 65° C. into the first barrel of this same extruder. Separately from this, plasticizer 1 is metered at a charge temperature of 40° C. into a downstream barrel in the final third of this same extruder. The speed of the twin screw was 280 rpm. The set temperature values for the barrels in the downstream direction were 190° C. in the first third of the screw and 170° C. in the second and third thirds of the screw. The output was 600 kg/h. In this way, the thermoplastic polyurethane (TPU) is synthesized in the known reaction extruder process. The pelletizable reaction melt thus obtained can be formed into lenticular pellets in the subsequent process—what is known as underwater pelletization. The pellets are dried by subsequent aftertreatment at approximately 80 to 90° C. and they are thereafter packaged in transportable containers.

[0184] The TPU pellets thus obtained are pre-dried at 80 to 100° C. for 3 h prior to further processing, and then formed into test specimens by injection molding. The zone temperatures of the injection molding units used for this purpose are between 190° C. and 220° C. S2 test bars are stamped out from the specimen panels thus obtained and are subjected to further mechanical tests. In addition, the chemical values, such as for example molar mass, of these test specimens are determined.

2.4 Production Process 4—(Single-Stage Reactive Extrusion Process with P1+a Polyol), Process for Continuous Synthesis of Comparative Example 4 and Examples 1, 2, 4, 5, 6 And 7

[0185] A mixture of CE1, processing auxiliary 1, stabilizer 1 and polyol 2, on the one hand, was metered at a charge temperature of 150° C. into the first barrel of a ZSK 92 twin-screw extruder from Werner & Pfleiderer, Stuttgart, having a processing length of 56 D and, separately from this, isocyanate 1 was metered at a charge temperature of 65° C. into the first barrel of this same extruder. Separately from this, plasticizer 1 is metered at a charge temperature of 40° C. into a downstream barrel in the final third of this same extruder. The speed of the twin screw was 280 rpm. The set temperature values for the barrels in the downstream direction were 190° C. in the first third of the screw and 170° C. in the second and third thirds of the screw. The output was 600 kg/h. In this way, the thermoplastic polyurethane (TPU) is synthesized in the known reaction extruder process. The pelletizable reaction melt thus obtained can be formed into lenticular pellets in the subsequent process—what is known as underwater pelletization. The pellets are dried by subsequent aftertreatment at approximately 80 to 90° C. and they are thereafter packaged in transportable containers.

[0186] The TPU pellets thus obtained are pre-dried at 80 to 100° C. for 3 h prior to further processing, and then formed into test specimens by injection molding. The zone temperatures of the injection molding units used for this purpose are between 190° C. and 220° C. S2 test bars are stamped out from the specimen panels thus obtained and are subjected to further mechanical tests. In addition, the chemical values, such as for example molar mass, of these test specimens are determined.

[0187] The synthesis and properties of the thermoplastic polyurethanes obtained are summarized in tables 4, 5, 6 and 7. The samples produced using these processes serve as comparative examples 3 and 4 and also examples 1, 2, 4, 5, 6 and 7.

TABLE-US-00004 TABLE 4 Synthesis of comparative examples 3 + 4: Comparative Comparative example 3 example 4 Polyol 1 [g] 500 Polyol 2 [g] 500 1000 Isocyanate 1 [g] 295 295 CE 1 [g] 35.6 59.0 Stabilizer 1 [g] 15.8 16.1 Plasticizer 1 [g] 237.6 241.8 Processing auxiliary 1 [g] <1 <1 Index 1030 1022

TABLE-US-00005 TABLE 5 Properties of comparative examples 3 + 4: Comparative Comparative example 3 example 4 Shore A 65 64 Tensile strength [MPa] 34 23 Elongation at break [%] 700 590 Tear propagation resistance 42 31 [kN/m] Abrasion [mm.sup.3] 39 31 GPC molar mass [10.sup.3 daltons] 200 257

TABLE-US-00006 TABLE 6 Synthesis of examples 1, 2, 3, 4, 5, 6 and 7: Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Polyol 1 [g] 850 Dry Dry Dry Polyol 2 [g] 1000 1000 150 blend of blend of blend of 1000 Isocyanate 1 [g] 295 295 340 comparative comparative comparative 295 CE 1 [g] 61.6 61.3 70.6 example example example 61.3 Stabilizer 1 [g] 16.1 16.1 16.8 4 & 4 & 4 & 16.1 Plasticizer 1 [g] 242.2 242.2 251.9 example example example 242.2 PA1 [g] <1 <1 <1 1 (mass 1 (mass 1 (mass <1 Index 1009 1012 1020 ratio 2:1) ratio 1:1) ratio 1:2) 1000 Calculated index 1016 1013 1007

TABLE-US-00007 TABLE 7 Properties of examples 1, 2, 3, 4, 5, 6 and 7: Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Shore A 62 62 66 63 63 61 62 Tensile strength 37 38 28 41 33 33 32 [MPa] Elongation at break 990 990 650 960 860 880 740 [%] Tear propagation 41 44 32 40 40 44 44 resistance [kN/m] Abrasion [mm.sup.3] 40 38 35 32 35 38 30 GPC molar mass 150 160 248 233 211 180 155 [10.sup.3 daltons]

[0188] Molded articles (M-1) were produced from the TPU pellet materials described (examples and comparative examples) in an injection molding process. To this end, the pellets are pre-dried at 80 to 100° C. for 3 h before injection molding and then formed into the molded article (M-1) by injection molding. The zone temperatures of the injection molding units used for this are between 190° C. and 220° C. The molded article (M-1) obtained is optionally subjected to maturation (annealing by heat treatment, 10 h at 70° C.), as noted in table 8.

[0189] The final molded article (M) is produced in a number of substeps: [0190] a. the molded article (M-1), which has holes through which the water vapor can pass, is inserted into a mold of a water vapor molding machine from Kurtz (Boost Foamer) [0191] b. the foamed pellet material eTPU 1 is filled in [0192] c. the eTPU 1 is exposed to water vapor and subjected to welding with itself and with the molded article M-1 at a temperature of from 130 to 135° C. [0193] d. the final M is annealed at 70° C. for 4 hours.

[0194] The property characteristics described in table 8 were evaluated as follows: [0195] 1. The shape retention was evaluated visually on the molded article (M-1) after the molded article M had been obtained. The label “poor” denotes a change in the structure of M-1, such as for example in edge sharpness, deformation, gloss or flowing of the structure, which results in a deterioration in the visual appearance of the surface. [0196] 2. A 10 mm strip was cut out from the molded article M every two centimeters around it.

[0197] After a gap had been introduced into the molded article M, the adhesion was determined by measuring the tensile strength. To this end, the molded article M-1 and the welded pellet material were pulled apart in opposite directions at a rate of 100 mm/min in a tensile testing machine. “Good” denotes a sample which has a tensile strength in this test of greater than 2.7 N/mm. [0198] 3. The storage stability refers to the change in the TPU pellet material after synthesis but before processing. The label “poor” denotes excessive change in the sample consistency. [0199] 4. Process stability refers to the consistency of the process for producing M-1 and the change therein over time. The label “poor” denotes excessive change in the process consistency. [0200] 5. The thermomechanical analysis (TMA) was effected in accordance with ISO 11359 (2014), heating rate 20 K/min, weight 15 g, round ram of diameter 3 mm, TPU sample geometry: diameter 4 mm and thickness 2 mm.

[0201] It was possible to determine two areas (zone (1) and zone (2), shown in FIG. 1), which are characteristic for the evaluation of the adhesion in the case of a process in which foamed particles are welded in the presence of a component, or of the shape retention of the contours of the components.

TABLE-US-00008 TABLE 8 Production of the molded article (M) from, inter alia, eTPU 1. GPC* Annealing Index Crosslinker 1 Molar Evaluation of M-1 by of the present in mass TMA Shape Storage Process heat treatment TPU TPU [kD] Zone 1 Zone 2 retention Adhesion stability stability (10 h at 70° C.) Comparative ex. 1 1010 — 125 no yes poor good good good Required Comparative ex. 2 1010 1.5 260 yes yes good good good poor Required Comparative ex. 3 1030 — 200 no yes poor good poor good Not required Comparative ex. 4 1022 — 257 yes no good poor poor good Not required Example 1 1009 — 150 yes yes good good good good Not required Example 2 1012 — 160 yes yes good good good good Not required Example 3 1020 — 248 good good poor good Not required Example 4 1016 — 233 yes yes good good poor good Not required Example 5 1013 — 211 yes yes good good poor good Not required Example 6 1007 — 180 yes yes good good poor good Not required Example 7 1000 — 155 good good good good Not required *of matured material (6 weeks at RT)

[0202] The results show that good products are obtained using a thermoplastic polyurethane based on PTHF with an Mn>1500 g/mol and an index of 1020 is not exceeded during the production.

[0203] As shown by comparative example 2 in particular, when using crosslinker 1, the high sensitivity of crosslinker 1 results in problems in production which are reflected, for example, in shrinkage of the sole. This means that the soles have to undergo additional heat treatment, which is more expensive. The heat treatment of the soles (M-1) was adapted for these samples so that when producing the final molded article M the soles no longer exhibit any change in shape and that the shrinkage of M-1 is less pronounced. To this end, these samples are heat treated at 70° C. for 10 h. [0204] 3. Measurement methods/standards: [0205] Shore A: DIN ISO 7619-1 (February 2012) [0206] Tensile strength DIN 53504 (March 2017), national for Germany, international DIN EN ISO 527-2 (June 2012) [0207] Elongation at break DIN 53504 (March 2017), national for Germany, international DIN EN ISO 527-2 (June 2012) [0208] Tear propagation resistance: (with notch) DIN ISO 34-1, B (b) (September 2016) [0209] Abrasion determination DIN ISO 4649 (March 2014) [0210] Gel permeation chromatography (GPC): DIN 55672-2 (2008), samples were completely dissolved at 80° C. to 0.5% in amine-containing DMF beforehand. DMF was also used as flow agent. [0211] Thermomechanical analysis (TMA): ISO 11359 (2014), heating rate 20 K/Min, weight 15 g, round ram of diameter 3 mm, TPU sample geometry: diameter 4 mm and thickness 2 mm

LITERATURE CITED

[0212] Ullmann's “Encyklopädie der technischen Chemie” [Encyclopedia of Industrial Chemistry], 4th edition, volume 20, pp. 416 ff [0213] WO 94/20568 A1 [0214] WO 2007/082838 A1 [0215] “Polymer Chemistry”, Interscience Publ., New York, 1961, pp. 111-127 [0216] “Kunststoffhandbuch” [Plastics handbook], volume VIII. C. Hanser Verlag, Munich 1973 Journal of Polymer Science, Part A1, 4, pages 1851-1859 (1966) [0217] Kunststoffhandbuch, volume 7, “Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapter 3.1 [0218] Kunststoffhandbuch, volume VII. Vieweg and Höchtlen, Carl Hanser Verlag, 1966, pp. 103-113 [0219] WO 2007/118827 A1