CN111218101B - High-strength fatigue-resistant thermoplastic polyurethane elastomer composition and preparation method and application thereof - Google Patents
High-strength fatigue-resistant thermoplastic polyurethane elastomer composition and preparation method and application thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention relates to a high-strength fatigue-resistant thermoplastic polyurethane elastomer composition, a preparation method and application thereof, wherein the composition comprises the following components in parts by weight: 40-99 parts of thermoplastic polyurethane elastomer and 1-60 parts of hyperbranched polymer, wherein the hyperbranched polymer is a hyperbranched polymer with a terminal unit containing a reactive group. The thermoplastic polyurethane elastomer composition has excellent mechanical strength, elastic property and fatigue resistance, and the preparation process is simple and easy to operate. Can be widely applied to the automobile industry, the mechanical industry, the medical industry, the transportation and the articles for daily use.
Description
Technical Field
The invention belongs to the field of thermoplastic elastomer composite materials, and particularly relates to a thermoplastic polyurethane elastomer composition, and a preparation method and application thereof.
Background
Thermoplastic polyurethane elastomer (TPU) is a thermoplastic elastomer that can be melt processed. The microstructure is a microphase separation structure consisting of a hard segment phase formed by the reaction of a chain extender and diisocyanate and a soft segment phase obtained by the reaction of a polyol and diisocyanate. The soft and hard segments exhibit an ordered, disordered arrangement in their respective phases. It can maintain high elasticity in a wide hardness range, has good mechanical strength and wear resistance, and has excellent oil resistance, aging resistance and the like.
TPU is widely applied to industries such as automobile industry, mechanical industry, medical industry, transportation, sports goods and the like as an elastomer material capable of being subjected to thermoplastic melt processing. With the progress of the times, the requirements on the performance of TPU are more and more severe. In order to meet the further requirements of mechanical properties and fatigue resistance of TPU under severe conditions, upgrading and improving of TPU are generally required.
Patent CN 106220808A provides a method for synthesizing a bending-resistant thermoplastic polyurethane elastomer, and patent CN 107474210 a discloses a method for synthesizing a bending-resistant and flexing-resistant thermoplastic polyurethane elastomer.
Patent CN 105111716A discloses a flex-resistant and fatigue-resistant thermoplastic elastomer material and a preparation method thereof. The invention is prepared by mixing various polymers, including thermoplastic polyurethane elastomer, styrene-ethylene-propylene-styrene block copolymer, metallocene ethylene-octene copolymer, hydroxyl-terminated polybutadiene and the like, and filler components, including organic montmorillonite, Shengma fiber, oxidized graphene, porcelain powder and the like.
Hyperbranched polymers are a class of highly branched polymers with three-dimensional stereo architecture. Can be used in the fields of coating, paint, polymer processing aid, optical material, functional film material, drug slow release and the like.
Patent CN 1966544A describes a preparation method of hyperbranched polyurethane. Patent CN 1385450A introduces a hyperbranched polyurethane with controllable branching degree and a preparation method thereof. Patent CN 105778030 a application of hyperbranched polyamine-ester in modifying polyurethane leather slurry yellowing resistance.
Patent CN 103242627 a, describes adding fatty acid ester-terminated hyperbranched polyester to thermosetting polyurethane prepolymer, epoxy resin prepolymer or thermoplastic polyolefin or polyester, and adjusting the content of fatty acid ester-terminated hyperbranched polyester to adjust the viscosity and strength of the blended material.
TPU compositions having excellent mechanical properties and fatigue resistance are prepared by blending TPU with hyperbranched polymers.
Disclosure of Invention
The invention aims to provide a thermoplastic polyurethane elastomer (TPU) composition and a preparation method thereof, wherein the TPU composition has excellent mechanical strength, elastic property and fatigue resistance, and the preparation process is simple and easy to operate.
A high strength, fatigue resistant thermoplastic polyurethane elastomer composition, said composition comprising:
40-99 parts by weight of a thermoplastic polyurethane elastomer,
1 to 60 parts by weight of a hyperbranched polymer,
it is further preferred that the components of the composition,
50-95 parts by weight of a thermoplastic polyurethane elastomer,
5-50 parts by weight of a hyperbranched polymer,
the hyperbranched polymer is a hyperbranched polymer of which the terminal unit contains a reactive group, and the total weight of the thermoplastic polyurethane elastomer and the hyperbranched polymer is 100 parts by weight.
The hyperbranched polymer can be one or more of hyperbranched polyurethane, hyperbranched polyacrylate, hyperbranched polyamide, hyperbranched polyurethane-acrylate, hyperbranched polyamide-ester, hyperbranched polyamide-amine, hyperbranched polycarbonate, hyperbranched polyetherketone, hyperbranched polyphosphate, hyperbranched polysiloxane, hyperbranched epoxy resin, hyperbranched cyclodextrin, hyperbranched polycarbazole, hyperbranched polylactic acid, hyperbranched polysulfonamine, hyperbranched polyethernitrile, hyperbranched polyether, hyperbranched polyphenyl, hyperbranched polyethylene glycol and the like, preferably hyperbranched polyester, hyperbranched polyurethane, hyperbranched polyamide-amine, hyperbranched polyamide-ester, hyperbranched epoxy resin, hyperbranched polyacrylate, hyperbranched polysiloxane, hyperbranched poly (acrylic acid), One or more of hyperbranched polyethylene glycol.
The reactive group contained in the terminal unit of the hyperbranched polymer may specifically be one or more of a hydroxyl group, an amino group, an arylamine group, a carboxyl group, benzoic acid, a thiol group, an azide group, an allyl group, an ethynyl group, an epoxy group, a saturated fatty acid, an unsaturated fatty acid, and the like, and preferably one or more of a hydroxyl group, an amino group, a carboxyl group, an allyl group, an ethynyl group, a saturated fatty acid, an unsaturated fatty acid, and the like.
In the thermoplastic polyurethane elastomer composition of the present invention, the number of the reactive groups of the terminal unit of the hyperbranched polymer is 2 to 5000, preferably 4 to 2000, and more preferably 4 to 512.
Preferably, the molecular weight of the hyperbranched polymer is 200-.
The hardness of the thermoplastic polyurethane elastomer in the thermoplastic polyurethane elastomer composition is between 75A Shore and 85D Shore, and preferably between 80A Shore and 78D Shore.
Preferably, the hard segment of the thermoplastic polyurethane elastomer in the thermoplastic polyurethane elastomer composition is composed of diisocyanate and a chain extender; wherein, the diisocyanate is one, two or more of TDI, MDI, HMDI, HDI, PPDI, IPDI, NDI, XDI, TTI, TODI and the like; preferably one, two or more of TDI, MDI, HMDI, HDI and IPDI;
the chain extender is a small-molecular diamine or a dihydric alcohol, wherein the small-molecular diamine is preferably one or more of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, 3, 5-diamino isobutyl p-chlorobenzoate, diethyl toluene diamine and 3, 5-dimethyl sulfur toluene diamine, and the small-molecular dihydric alcohol is preferably one or more of 1, 4-butanediol, ethylene glycol, propylene glycol, methyl propylene glycol, diethylene glycol, 1, 4-cyclohexanediol and neopentyl glycol;
the soft segment phase of the thermoplastic polyurethane elastomer is composed of polyester polyol or polyether polyol; wherein, the polyester polyol is preferably one or more of alkyd polyester polyol, polycaprolactone polyol and polycarbonate polyol. The polyether polyol is preferably one or more of polypropylene oxide polyol, polytetrahydrofuran polyol and polyether polyol copolymer.
The invention further provides a preparation method of the high-strength fatigue-resistant thermoplastic polyurethane elastomer composition, which comprises the following steps: firstly, uniformly mixing the thermoplastic polyurethane elastomer and the hyperbranched polymer, and then carrying out melt blending on the mixture by any one of an open mill, an internal mixer, a kneader and an extruder to prepare the thermoplastic polyurethane elastomer and the hyperbranched polymer; wherein, the extrusion temperature of the extruder is preferably controlled between 160 ℃ and 230 ℃.
The invention also provides application of the high-strength fatigue-resistant thermoplastic polyurethane elastomer composition in the automobile industry, the mechanical industry, the medical industry, transportation or articles for daily use.
By adopting the technical scheme, the invention has the following beneficial effects:
1. a tensile strength (ASTM D412) that is increased by more than 50% over a corresponding unmodified thermoplastic polyurethane elastomer; the tearing performance (ASTM D624) is improved by more than 25 percent compared with the corresponding unmodified thermoplastic polyurethane elastomer.
2. The elasticity (impact resilience, ASTM D1054 and compression set, ASTM D395) is improved by more than 30% compared with that of the corresponding unmodified thermoplastic polyurethane elastomer.
3. The fatigue resistance (bending resistance, ASTM D1052) is improved by more than 1 time compared with the corresponding unmodified thermoplastic polyurethane elastomer.
Detailed Description
The invention is further illustrated by the following specific examples. In the present application, parts, wt% are generally by mass unless otherwise specified.
Example 1
The hyperbranched polymer is selected from hyperbranched polyamide, the addition amount is 5 parts, and the molecular weight is 350 g/mol. The terminal unit has amino group as the reactive functional group and 4 reactive functional groups (available from Wuhan super-branched resin science and technology Co., Ltd., HyPer N101).
The mixture was mixed with 95 parts of a polyether thermoplastic polyurethane elastomer (commercially available) having a hardness of 80A uniformly in a high-speed mixer, and the mixture was melt-blended and extruded in an extruder having an extrusion temperature of 170 and 190 ℃ to obtain a TPU composition.
Example 2
The hyperbranched polymer is selected from hyperbranched polyamide-amine, the addition amount is 15 parts, and the molecular weight is 116000 g/mol. The terminal unit of the functional group is amino, the number of the reactive functional groups is 512 (from Wehaichen molecular New Material Co., Ltd., trade name of CDY-170A).
The mixture and 85 parts of polyether type thermoplastic polyurethane elastomer (sold in the market) with the hardness of 60D are evenly mixed on a high-speed mixer, and the mixture is melted, blended and extruded on an extruder with the extrusion temperature of 200 and 220 ℃ to obtain the TPU composition.
Example 3
The hyperbranched polymer is hyperbranched epoxy resin, the adding amount is 30 parts, and the molecular weight is 3200 g/mol. The terminal unit has hydroxyl group as the reactive functional group and 4 reactive functional groups (available from Wuhan super-branched resin science and technology Co., Ltd., HyPer E102).
The mixture was mixed with 70 parts of a polyester type thermoplastic polyurethane elastomer (commercially available) having a hardness of 80A uniformly in a high-speed mixer, and the mixture was melt-blended and extruded in an extruder having an extrusion temperature of 170 and 195 ℃ to obtain a TPU composition.
Example 4
The hyperbranched polymer is selected from hyperbranched polysiloxane, the addition amount is 50 parts, and the molecular weight is 6500 g/mol. The reaction functional group of the terminal unit is hydroxyl, the number of the reaction functional group is 30-32, (purchased from Wuhan super-branched resin science and technology Co., Ltd., the mark is HyPer HPS 603).
The mixture was mixed with 50 parts of a polyester type thermoplastic polyurethane elastomer (commercially available) having a hardness of 95A uniformly in a high-speed mixer, and the mixture was melt-blended and extruded in an extruder having an extrusion temperature of 200 and 220 ℃ to obtain a TPU composition.
Example 5
The hyperbranched polymer is selected from hyperbranched polyamide-ester, the addition amount is 5 parts, and the molecular weight is 2500 g/mol. The number of the reactive functional groups in the terminal unit was 8 in total (available from Polymer factory, Inc. under the trade name hybrid PS 2800).
The mixture was mixed with 95 parts of a polyester type thermoplastic polyurethane elastomer (commercially available) having a hardness of 78D uniformly in a high-speed mixer, and the mixture was melt-blended and extruded in an extruder having an extrusion temperature of 210 ℃ and 235 ℃ to obtain a TPU composition.
Example 6
The hyperbranched polymer is selected from hyperbranched polyamide-ester, the addition amount is 5 parts, and the molecular weight is 2500 g/mol. The reactive functional groups of the terminal units were 50% hydroxyl and 50% saturated stearic acid, and the total number of reactive functional groups was 8 (available from Polymer factory, under the brand name hybrid PS 2550).
The mixture was mixed with 95 parts of a polyester type thermoplastic polyurethane elastomer (commercially available) having a hardness of 78D uniformly in a high-speed mixer, and the mixture was melt-blended and extruded in an extruder having an extrusion temperature of 210 ℃ and 235 ℃ to obtain a TPU composition.
Example 7
The hyperbranched polymer is selected from hyperbranched functional polyethylene glycol, the addition amount is 25 parts, and the molecular weight is 22000 g/mol. The terminal unit of the copolymer had an ethynyl group as a reactive functional group, and the total number of reactive functional groups was 16 (available from Polymer factory under the trademark PFD-G3-PEG 20K-Acetylence).
The mixture was mixed with 75 parts of a polyester type thermoplastic polyurethane elastomer (commercially available) having a hardness of 64D uniformly in a high-speed mixer, and the mixture was melt-blended and extruded in an extruder having an extrusion temperature of 210 ℃ and 230 ℃ to obtain a TPU composition.
Example 8
The hyperbranched polymer is selected from hyperbranched polyacrylate, the addition amount is 40 parts, and the molecular weight is 1200 g/mol. The terminal unit has carboxyl as the reactive functional group and 6-8 reactive functional groups (available from Changxing chemical industries, Ltd., Eternal-6361-.
The mixture was mixed with 60 parts of a polyester type thermoplastic polyurethane elastomer (commercially available) having a hardness of 85A uniformly on a high-speed mixer, and the mixture was melt-blended and extruded on an extruder having an extrusion temperature of 195-215 ℃ to obtain a TPU composition.
Example 9
The hyperbranched polymer is selected from hyperbranched polyester, the addition amount is 45 parts, and the molecular weight is 700 g/mol. The reactive functional group of the terminal unit was an unsaturated fatty acid, and the total number of reactive functional groups was 4 (available from Polymer factory, Inc. under the trade name Boltorn U3000).
The mixture was mixed with 55 parts of a polyester type thermoplastic polyurethane elastomer having a hardness of 90A (commercially available) uniformly in a high-speed mixer, and the mixture was melt-blended and extruded in an extruder having an extrusion temperature of 190-.
Example 10
The hyperbranched polymer is selected from hyperbranched polyester, the addition amount is 10 parts, and the molecular weight is 2100 g/mol. The reactive functional group of the terminal unit was Allyl, and the total number of reactive functional groups was 16 (available from Polymer factory, under the trademark PFD-G4-NHBOC-Allyl).
The mixture was mixed with 90 parts of a polyester type thermoplastic polyurethane elastomer (commercially available) having a hardness of 90A uniformly in a high-speed mixer, and the mixture was melt-blended and extruded in an extruder having an extrusion temperature of 190-.
Example 11
The hyperbranched polymer is selected from hyperbranched polyester, the addition amount is 45 parts, and the molecular weight is 700 g/mol. The reactive functional group of the terminal unit is hydroxyl, and the total number of the reactive functional groups is 6 (purchased from Wuhan super-branched resin science and technology Limited company, and the mark is HyPer H30-H301).
The mixture and 55 parts of polyester type thermoplastic polyurethane elastomer (commercially available) with the hardness of 90A are evenly mixed on a high-speed mixer, and the mixture is melted, blended and extruded on an extruder with the extrusion temperature of 190 and 200 ℃ to obtain the TPU composition.
Comparative example 1
The same polyether type thermoplastic polyurethane elastomer (hardness 80A) as in example 1 was selected as comparative example 1.
Comparative example 2
The same polyether type thermoplastic polyurethane elastomer (hardness 54D) as in example 2 was selected as comparative example 2.
Comparative example 3
The same polyester type thermoplastic polyurethane elastomer (hardness 80A) as in example 3 was selected as comparative example 3.
Comparative example 4
The same polyester type thermoplastic polyurethane elastomer (hardness 85A) as in example 4 was selected as comparative example 4.
Comparative example 5
The same polyester type thermoplastic polyurethane elastomer (hardness 95A) as in example 5 was selected as comparative example 5.
Comparative example 6
The same polyester type thermoplastic polyurethane elastomer (hardness 78D) as in example 6 was selected as comparative example 6.
Comparative example 7
The same polyester type thermoplastic polyurethane elastomer (hardness 64D) as in example 7 was selected as comparative example 7.
Comparative example 8
The same polyester type thermoplastic polyurethane elastomer (hardness 90A) as in example 8/9/10/11 was selected as comparative example 8.
Comparative example 9
The hyperbranched polymer is selected from hyperbranched polyamide-amine, the addition amount is 15 parts, and the molecular weight is 116000 g/mol. The terminal unit of the functional group is amino, the number of the reactive functional groups is 512 (from Wehaichen molecular New Material Co., Ltd., trade name of CDY-170A).
The two components are uniformly mixed with 85 parts of thermoplastic polystyrene (sold in the market) on a high-speed mixer, and the mixture is melted, blended and extruded on an extruder with the extrusion temperature of 190 ℃ and 240 ℃ to obtain the two components.
Comparative example 10
The same polystyrene as in comparative example 9 was used as comparative example 10.
Comparative example 11
The hyperbranched polymer is hyperbranched epoxy resin, the addition amount is 30 parts, and the molecular weight is 3200 g/mol. The terminal unit has hydroxyl as the reactive functional group and 4 reactive functional groups (available from Wuhan super-branched resin science and technology Co., Ltd., HyPer E102).
The mixture and 70 parts of thermoplastic polymethyl methacrylate (sold in market) are mixed evenly on a high-speed mixer, and the mixture is melted, blended and extruded on an extruder with the extrusion temperature of 170-195 ℃, so as to obtain the TPU composition.
Comparative example 12
The same polymethyl methacrylate as in comparative example 11 was used as comparative example 12.
The data for the examples and comparative examples are as follows:
Claims (16)
1. a high strength, fatigue resistant thermoplastic polyurethane elastomer composition, said composition consisting of:
40-99 parts by weight of a thermoplastic polyurethane elastomer,
1 to 60 parts by weight of a hyperbranched polymer,
the hyperbranched polymer is a hyperbranched polymer of which the terminal unit contains a reactive group, and the total weight of the thermoplastic polyurethane elastomer and the hyperbranched polymer is 100 parts by weight;
the hyperbranched polymer is selected from one or more of hyperbranched polyurethane, hyperbranched polyacrylate, hyperbranched polyamide, hyperbranched polyurethane-acrylate, hyperbranched polyamide-ester, hyperbranched polyamide-amine, hyperbranched polycarbonate, hyperbranched polyether ketone, hyperbranched polyphosphate, hyperbranched polysiloxane, hyperbranched epoxy resin, hyperbranched poly-cyclodextrin, hyperbranched polycarbazole, hyperbranched polylactic acid, hyperbranched polysulfone amine, hyperbranched polyether nitrile, hyperbranched polyether and hyperbranched polyphenyl;
the reactive group contained in the terminal unit of the hyperbranched polymer is selected from one or more of hydroxyl, amino, arylamine group, benzoic acid, thiol group, azide group, allyl, ethynyl, epoxy group and unsaturated fatty acid.
2. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition of claim 1, wherein: the composition is composed of (A) a mixture of (A) and (B),
50-95 parts by weight of a thermoplastic polyurethane elastomer,
5-50 parts of hyperbranched polymer.
3. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition of claim 1, wherein: the hyperbranched polymer is selected from one or more of hyperbranched polyurethane, hyperbranched polyamide-amine, hyperbranched polyamide-ester, hyperbranched epoxy resin, hyperbranched polyacrylate, hyperbranched polysiloxane and hyperbranched polyethylene glycol.
4. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein:
the number of the reaction groups of the hyperbranched polymer terminal unit is 2-5000.
5. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition of claim 4, wherein: the reactive group contained in the terminal unit of the hyperbranched polymer is selected from one or more of hydroxyl, amino, allyl, ethynyl and unsaturated fatty acid; and/or
The number of the reaction groups of the hyperbranched polymer terminal unit is 4-2000.
6. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition of claim 5, wherein:
the number of the reaction groups of the hyperbranched polymer terminal unit is 4-512.
7. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein:
the molecular weight of the hyperbranched polymer is 200-200000 g/mol.
8. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition of claim 7, wherein:
the molecular weight of the hyperbranched polymer is 350-116000 g/mol.
9. The high strength fatigue resistant thermoplastic polyurethane elastomer composition according to claim 1 or 2, characterized in that:
the tensile strength of the thermoplastic polyurethane elastomer composition according to ASTM D412 is improved by more than 50 percent compared with that of the corresponding unmodified thermoplastic polyurethane elastomer; the tearing performance according to ASTM D624 is improved by more than 25 percent compared with the corresponding unmodified thermoplastic polyurethane elastomer;
the elasticity of the thermoplastic polyurethane elastomer composition, namely the impact resilience according to ASTM D1054 and/or the compression set according to ASTM D395, is improved by more than 30 percent compared with the corresponding unmodified thermoplastic polyurethane elastomer;
the fatigue resistance of the thermoplastic polyurethane elastomer composition is improved by more than 1 time compared with that of a corresponding unmodified thermoplastic polyurethane elastomer according to the bending resistance of ASTM D1052.
10. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein:
the hardness of the thermoplastic polyurethane elastomer in the thermoplastic polyurethane elastomer composition is between 75A and 85D Shore.
11. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition of claim 10, wherein:
the hardness of the thermoplastic polyurethane elastomer in the thermoplastic polyurethane elastomer composition is between 80A and 78D.
12. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein:
the hard segment of the thermoplastic polyurethane elastomer in the thermoplastic polyurethane elastomer composition consists of diisocyanate and a chain extender; wherein, the diisocyanate is one or more of TDI, MDI, HMDI, HDI, PPDI, IPDI, NDI, XDI, TTI and TODI;
the chain extender is micromolecular diamine or dihydric alcohol;
the soft segment phase of the thermoplastic polyurethane elastomer is composed of polyester polyol or polyether polyol.
13. The high strength, fatigue resistant thermoplastic polyurethane elastomer composition of claim 12, wherein:
the diisocyanate is one or more of TDI, MDI, HMDI, HDI and IPDI;
the small molecular diamine is selected from one or more of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, 3, 5-diamino isobutyl p-chlorobenzoate, diethyl toluene diamine and 3, 5-dimethyl sulfur toluene diamine, and the small molecular diol is selected from one or more of 1, 4-butanediol, ethylene glycol, propylene glycol, methyl propylene glycol, diethylene glycol, 1, 4-cyclohexanediol and neopentyl glycol;
the polyester polyol is selected from one or more of alkyd polyester polyol, polycaprolactone polyol and polycarbonate polyol; the polyether polyol is one or more selected from polypropylene oxide polyol, polytetrahydrofuran polyol and polyether polyol copolymer.
14. A method for preparing a high strength, fatigue resistant thermoplastic polyurethane elastomer composition as defined in any one of claims 1 to 13, comprising the steps of:
the thermoplastic polyurethane elastomer and the hyperbranched polymer are uniformly mixed and then are subjected to melt blending through any one of an open mill, an internal mixer, a kneading machine and an extruder to prepare the thermoplastic polyurethane elastomer.
15. The method as claimed in claim 14, wherein the extrusion temperature of the extruder is controlled to be between 160 ℃ and 230 ℃.
16. Use of the high strength, fatigue resistant thermoplastic polyurethane elastomer composition according to any of claims 1 to 13 in the automotive industry, the mechanical industry, the medical industry, transportation, or household goods.
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