Thermoplastic polyurethane elastomer, preparation method of thermoplastic polyurethane elastomer, thermoplastic polyurethane elastomer insole material and preparation method of thermoplastic polyurethane elastomer insole material

Abstract

The thermoplastic polyurethane elastomer is prepared from the following raw materials in parts by weight: 30 to 45 parts of polyester polyol, 15 to 40 parts of polyether polyol, 0.4 to 0.8 part of UV (Ultraviolet)-resistant agent, 0.2 to 0.5 part of antioxidant, 20 to 30 parts of isocyanate, 3 to 5 parts of nucleating agent and 8 to 12 parts of chain extender. The raw material monomer is derived from plants and has the characteristics of low carbon and sustainability, the preparation process has large-scale potential, and the material performance is excellent. The supercritical foaming insole material prepared from the elastomer has high elasticity, low temperature resistance and environmental friendliness, and the selection range of high-performance physical foaming raw materials is widened.

Description

Technical Field

[0001] The present specification relates to the technical field of footwear products, and in particular to a thermoplastic polyurethane elastomer and a preparation method thereof, a thermoplastic polyurethane elastomer midsole material and a preparation method thereof. Background Art

[0002] Thermoplastic polyurethane elastomer (TPU) is a polymer composed of flexible soft segments and rigid hard segments. It has both rubber elasticity and high temperature plastic molding, and has excellent mechanical properties. Thanks to the excellent yellowing resistance, high rebound and wear resistance of aliphatic TPU, some sports brands have applied it to shoes.

[0003] In the context of low carbon and green development, the synthesis of polymer materials from monomers derived from biomass raw materials is a major trend. Bio-based polyurethane is a polymer made from renewable resources, which has good sustainability and environmental protection, and therefore has attracted much attention.

[0004] Chinese patent CN 115975385 A effectively improves the compression deformation resistance and tear strength of nylon elastomer by adding nylon resin and chain extender to the long-chain nylon elastomer matrix, and uses hyperbranched resin as a dispersant to finally obtain a nylon elastomer foam material with light weight, good resilience, excellent compression deformation resistance and tear resistance. Chinese patent CN 108250734A blends Pebax and TPU to prepare a supercritical fluid foam material, which can make up for the shortcomings of the two materials. The density of the blended material can be lower and the hardness does not change much, thereby obtaining an ultra-light, high-elastic, high-strength foam material. It solves the problems of TPU material products with high density and easy shrinkage, poor water resistance, poor weather resistance, and easy yellowing. Chinese patent CN 115725074 A prepares a polyamide elastomer with bio-based long carbon chain polyamide as the hard segment. The raw material monomer is derived from plants, has the characteristics of low carbon and sustainable development, can adjust the hardness in the range of 20D-80D, and has a lower density than polyurethane elastomers and polyester elastomers.

[0005] At present, the top high-elastic midsole materials on the market are nylon elastomer materials (PEBA) and aliphatic TPU materials. Most of them are derived from petroleum-based materials, and PEBA raw materials are expensive, and the prepared foam materials have insufficient tear strength. Long-chain nylon elastomers have high technical barriers and high costs. Ordinary polyurethane materials are difficult to achieve the comprehensive performance of high elasticity, yellowing resistance and light weight. With the increasing demand for lightweight materials for professional sports equipment, high-elasticity, low-density elastomer materials will have broad prospects. The synthesis of chemical raw materials with bio-based monomers is also a trend of sustainable development in the future. Expensive and overly single foaming raw materials cannot meet the diverse markets of shock absorption, lightweight, functionalization, and cost-effectiveness in the future. Summary of the invention

[0006] In order to solve the above technical problems, this application attempts to synthesize aliphatic polyurethane elastomers with similar long-chain structures using two bio-based diols, isosorbide and 1,3-propylene glycol. The raw material monomers are derived from plants, have low-carbon and sustainable characteristics, and the preparation process has the potential for large-scale production and excellent material performance. The supercritical foaming midsole material prepared from this elastomer has high elasticity, low-temperature resistance and environmental protection, which broadens the selection range of raw materials for high-performance physical foaming.

[0007] The present application provides a thermoplastic polyurethane elastomer, comprising the following raw materials in parts by weight: 30 to 45 parts of polyester polyol, 15 to 40 parts of polyether polyol, 0.4 to 0.8 parts of UV resistant agent, 0.2 to 0.5 parts of antioxidant, 20 to 30 parts of isocyanate, 3 to 5 parts of nucleating agent and 8 to 12 parts of chain extender.

[0008] The present application also provides a method for preparing the above-mentioned elastomer, comprising the following steps: (1) weighing polyester polyol, polyether polyol, UV resistant agent and antioxidant by weight, mixing and dissolving them to prepare a primary mixture; (2) weighing isocyanate, nucleating agent and chain extender, adding them to the primary mixture, stirring evenly, and melt-extruding to prepare a thermoplastic polyurethane elastomer.

[0009] The present application also provides a method for preparing a thermoplastic polyurethane elastomer midsole material, which is prepared using the above-mentioned thermoplastic polyurethane elastomer.

[0010] The present application also provides a thermoplastic polyurethane elastomer midsole material, which is prepared by the above-mentioned preparation method.

[0011] The beneficial effects brought by this application include but are not limited to: (1) More than 50% of the synthetic raw materials are biomass raw materials, which have good sustainability and environmental protection, and the formula ingredients are simple and have the potential for recycling. (2) Compared with the high-end midsole materials on the market, the midsole material has better rebound and lower compression deformation. The tear strength, tensile strength and compression deformation of the foamed material are better than the same type of aliphatic polyurethane materials on the market, and the cost of the raw materials will be lower than that of PEBAX raw materials, which broadens the selection range of high-performance physical foaming raw materials and can be applied to high-end sports shoe midsoles. (3) The polyurethane elasticity has the potential for other high-mechanical engineering applications. DETAILED DESCRIPTION

[0012] As shown in this specification and claims, unless the context clearly indicates an exception, the words "a", "an", "an" and / or "the" do not refer to the singular and may also include the plural. Generally speaking, the terms "comprise" and "include" only indicate the inclusion of the steps and elements that have been clearly identified, and these steps and elements do not constitute an exclusive list. The method or device may also include other steps or elements.

[0013] The present application provides a thermoplastic polyurethane elastomer, comprising the following raw materials in parts by weight: 30 to 45 parts of polyester polyol, 15 to 40 parts of polyether polyol, 0.4 to 0.8 parts of UV resistant agent, 0.2 to 0.5 parts of antioxidant, 20 to 30 parts of isocyanate, 3 to 5 parts of nucleating agent and 8 to 12 parts of chain extender.

[0014] In some embodiments, the thermoplastic polyurethane elastomer may include the following raw materials in parts by weight: 35-40 parts of polyester polyol, 20-35 parts of polyether polyol, 0.5-0.7 parts of UV resistant agent, 0.3-0.4 parts of antioxidant, 21.7-28.4 parts of isocyanate, 3-5 parts of nucleating agent and 8-12 parts of chain extender. In some embodiments, the thermoplastic polyurethane elastomer may include the following raw materials in parts by weight: 36-39 parts of polyester polyol, 22.5-32.5 parts of polyether polyol, 0.6 parts of UV resistant agent, 0.32-0.38 parts of antioxidant, 22-28 parts of isocyanate, 3-5 parts of nucleating agent and 9-10 parts of chain extender. In some embodiments, the thermoplastic polyurethane elastomer may include the following raw materials in parts by weight: 37-38 parts of polyester polyol, 25-30 parts of polyether polyol, 0.6 parts of UV resistant agent, 0.34-0.36 parts of antioxidant, 24-26 parts of isocyanate, 3-5 parts of nucleating agent and 9-10 parts of chain extender. In some embodiments, the thermoplastic polyurethane elastomer may include the following raw materials in parts by weight: 37-38 parts of polyester polyol, 27.5-30 parts of polyether polyol, 0.6 parts of UV resistant agent, 0.34-0.36 parts of antioxidant, 24-26 parts of isocyanate, 3-5 parts of nucleating agent and 9-10 parts of chain extender.

[0015] In some embodiments, the number average molecular weight of the polyester polyol can be 800 to 3000 g / mol. For example, the number average molecular weight of the polyester polyol can be about 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900 or 3000 g / mol. Any range characterized by a combination of the above end values ​​is also included, which will not be repeated here.

[0016] In some embodiments, the polyester polyol may be selected from one or more of polypropylene adipate, polypropylene suberate, polypropylene sebacate, polypropylene dodecanedioate, polyisosorbide adipate, polyisosorbide suberate, polyisosorbide sebacate or polyisosorbide dodecanedioate. In some embodiments, more preferably, the polyester polyol may be selected from polypropylene sebacate or polypropylene dodecanedioate.

[0017] In certain embodiments, the number average molecular weight of the polyether polyol can be 500-2000g / mol. For example, the number average molecular weight of the polyether polyol can be about 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900 or 2000g / mol. Also included are any ranges characterized by a combination of the above end values, which will not be repeated here. In certain embodiments, the polyether polyol can be selected from one or more of polytrimethylene ether glycol, polytetramethylene ether glycol, tetramethylene ether glycol-propylene oxide copolymer glycol or polypropylene glycol, polyoxypropylene glycol or polyoxypropylene triol. In certain embodiments, more preferably, the polyether polyol can be polytrimethylene ether glycol.

[0018] In some embodiments, the UV-resistant agent can be selected from UV-resistant agent 3280, titanium oxide, carbon black pigment, tetrakis(methylene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid)methane or PU836; in some embodiments, more preferably, the UV resistant agent can be UV resistant agent 3280.

[0019] In some embodiments, the antioxidant may be selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1098, and antioxidant 1076. In some embodiments, more preferably, the antioxidant may be antioxidant 1010.

[0020] In some embodiments, the isocyanate may be selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or 1,5-pentane diisocyanate. In some embodiments, preferably, the isocyanate may be hexamethylene diisocyanate.

[0021] In some embodiments, the nucleating agent may be selected from one or more of nano silicon dioxide, nano titanium dioxide, nano calcium carbonate, nano talc or nano zinc oxide. In some embodiments, preferably, the nucleating agent may be nano talc. In some embodiments, the chain extender may be an alcohol chain extender. In some embodiments, preferably, the chain extender may be 1,3-propylene glycol.

[0022] The present application also provides a method for preparing the above-mentioned elastomer, comprising the following steps: (1) weighing polyester polyol, polyether polyol, UV resistant agent and antioxidant by weight, mixing and dissolving them to prepare a primary mixture; (2) weighing isocyanate, nucleating agent and chain extender, adding them to the primary mixture, stirring evenly, and melt-extruding to prepare a thermoplastic polyurethane elastomer.

[0023] In some embodiments, the polyester polyol in step 1) may include the following raw materials in parts by weight: 45-50 parts of dibasic acid, 50-55 parts of diol, 0.005-0.015 parts of catalyst and 0.25-0.75 parts of antioxidant. In some embodiments, preferably, the polyester polyol may include the following raw materials in parts by weight: 45.8-47 parts of dibasic acid, 53-54.2 parts of diol, 0.008-0.012 parts of catalyst and 0.4-0.6 parts of antioxidant. In some embodiments, more preferably, the dibasic acid may be selected from one or more of succinic acid, adipic acid, sebacic acid, suberic acid or dodecanedioic acid, the diol may be selected from one or more of 1,3-propylene glycol, 1,4-butanediol, isosorbide or neopentyl glycol, the catalyst may be a tin catalyst, and the antioxidant may be selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1098 or antioxidant 1076. In some embodiments, further preferably, the dibasic acid may be selected from sebacic acid or dodecanedioic acid, and the diol may be selected from 1,3-propylene glycol or isosorbide.

[0024] In some embodiments, the polyester polyol may include the following raw materials in parts by weight: 45.8 to 47 parts of dibasic acid, 53 to 54.2 parts of diol, 0.01 parts of catalyst, and 0.5 parts of antioxidant.

[0025] In some embodiments, the polyester polyol in step 1) is prepared by a first-stage reaction and a second-stage reaction. In some embodiments, the first-stage reaction is heated under argon and stirring conditions, and reacts at 160-220°C until the acid value of the system is less than 30 mg KOH / g. In some embodiments, the first-stage reaction can be heated under argon and stirring conditions, and reacts at 165-215°C until the acid value of the system is less than 30 mg KOH / g. In some embodiments, the first-stage reaction can be heated under argon and stirring conditions, and reacts at 170-210°C until the acid value of the system is less than 30 mgKOH / g. In some embodiments, the first-stage reaction can be heated under argon and stirring conditions, and reacts at 175-205°C until the acid value of the system is less than 30 mg KOH / g. In some embodiments, the first-stage reaction can be heated under argon and stirring conditions, and reacts at 180-200°C until the acid value of the system is less than 30 mg KOH / g. In some embodiments, the first stage reaction may be heated under argon and stirring conditions, and react at 185-195° C. until the acid value of the system is less than 30 mg KOH / g. In some embodiments, the first stage reaction may be heated under argon and stirring conditions, and react at 185-190° C. until the acid value of the system is less than 30 mg KOH / g.

[0026] In some embodiments, the second stage reaction is to remove the water generated by the reaction under vacuum conditions of 220°C and 20-30Pa, terminate the reaction when the acid value of the system is lower than 1.0mg KOH / g, cool to 60-70°C and discharge the material to obtain polyester polyol. In some embodiments, the second stage reaction can be to remove the water generated by the reaction under vacuum conditions of 220°C and 22-28Pa, terminate the reaction when the acid value of the system is lower than 1.0mg KOH / g, cool to 62-68°C and discharge the material to obtain polyester polyol. In some embodiments, the second stage reaction can be to remove the water generated by the reaction under vacuum conditions of 220°C and 24-26Pa, terminate the reaction when the acid value of the system is lower than 1.0mg KOH / g, cool to 64-66°C and discharge the material to obtain polyester polyol.

[0027] In some embodiments, in step 2), the isocyanate and the primary mixed material are first transported to the pouring port of a twin-screw extruder, mixed evenly, and then extruded using a twin-screw extruder, extruded into a mold, and cured to obtain a thermoplastic polyurethane elastomer.

[0028] In some embodiments, the temperature of each reaction zone of the extruder is 110-130°C in zone 1, 140-160°C in zone 2, 160-180°C in zones 3, 4, and 5, 170-190°C in zones 6, 7, and 8, 180-200°C in zones 9 and 10, and the die head temperature is 190-210°C. In some embodiments, the temperature of each reaction zone of the extruder can be 112-128°C in zone 1, 142-158°C in zone 2, 158-178°C in zones 3, 4, and 5, 172-188°C in zones 6, 7, and 8, 182-198°C in zones 9 and 10, and the die head temperature is 192-208°C. In some embodiments, the temperature of each reaction zone of the extruder can be 114-126°C in zone 1, 144-156°C in zone 2, 160-176°C in zones 3, 4, and 5, 174-186°C in zones 6, 7, and 8, 184-196°C in zones 9 and 10, and the die temperature is 194-206°C. In some embodiments, the temperature of each reaction zone of the extruder can be 116-124°C in zone 1, 146-154°C in zone 2, 162-174°C in zones 3, 4, and 5, 176-184°C in zones 6, 7, and 8, 186-194°C in zones 9 and 10, and the die temperature is 196-204°C. In some embodiments, the temperature of each reaction zone of the extruder can be 118-122°C in zone 1, 148-152°C in zone 2, 164-172°C in zones 3, 4, and 5, 178-182°C in zones 6, 7, and 8, 188-192°C in zones 9 and 10, and the die temperature is 198-202°C. In some embodiments, the temperature of each reaction zone of the extruder can be 120-122°C in zone 1, 150-152°C in zone 2, 166-170°C in zones 3, 4, and 5, 180-182°C in zones 6, 7, and 8, 190-192°C in zones 9 and 10, and the die temperature is 200-202°C. In some embodiments, preferably, the temperature of each reaction zone of the extruder can be 120° C. in zone 1, 150° C. in zone 2, 170° C. in zones 3, 4, and 5, 180° C. in zones 6, 7, and 8, 190° C. in zones 9 and 10, and the die temperature is 200° C. In some embodiments, more preferably, a nucleating agent can be added to reaction zones 4 to 6, and a chain extender can be added to reaction zones 5 to 7.

[0029] In certain embodiments, the screw speed of the twin screw extruder is 300-500rpm. For example, the screw speed of the twin screw extruder may be about 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490 or 500rpm. Also included is any range characterized by a combination of the above end values, which will not be repeated here. In certain embodiments, preferably, the screw speed of the twin screw extruder may be 400rpm.

[0030] In some embodiments, the curing may be performed by cooling at room temperature.

[0031] The present application also provides a method for preparing a thermoplastic polyurethane elastomer midsole material, which is prepared using the above-mentioned thermoplastic polyurethane elastomer.

[0032] In some embodiments, the thermoplastic polyurethane elastomer is placed in a nitrogen supercritical fluid device to maintain pressure, and the high-elastic shock-absorbing foam material is obtained by internal leakage. In some embodiments, preferably, the pressure holding time can be 3 to 6 hours. For example, the pressure holding time can be about 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8 or 6 hours. It also includes any range characterized by a combination of the above end values, which will not be repeated here.

[0033] In some embodiments, preferably, the holding pressure may be 10 to 40 MPa. For example, the holding pressure may be about 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38 or 40 MPa. Any range characterized by a combination of the above end values ​​is also included, which will not be repeated here.

[0034] In some embodiments, preferably, the holding temperature may be 100-140° C. For example, the holding temperature may be about 100, 102, 104, 106, 108, 110, 112, 114, 116, 118, 120, 122, 124, 126, 128, 130, 132, 134, 136, 138 or 140° C. Any range characterized by a combination of the above end values ​​is also included, which will not be repeated here.

[0035] In some embodiments, preferably, the decompression time may be 0.5 to 1 hour. For example, the decompression time may be about 0.5, 0.6, 0.7, 0.8, 0.9 or 1 hour. Any range characterized by a combination of the above end values ​​is also included, which will not be repeated here.

[0036] In some embodiments, preferably, the pressure is released to a pressure of 1 to 3 MPa. For example, the pressure may be released to a pressure of about 1, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8 or 3 MPa. Any range characterized by a combination of the above end values ​​is also included, which will not be repeated here.

[0037] The present application also provides a thermoplastic polyurethane elastomer midsole material, which is prepared by the above-mentioned preparation method.

[0038] In some embodiments, the hardness of the midsole material is 35 to 39 degrees. For example, the hardness of the midsole material may be about 35, 36, 37, 38 or 39 degrees. Any range characterized by a combination of the above end values ​​is also included, which will not be repeated here.

[0039] In some embodiments, the density of the midsole material is 0.08-0.11 g / cm 3 In some embodiments, the density of the midsole material may be 0.09 to 0.10 g / cm 3 .

[0040] In some embodiments, the midsole material has a resilience of 79-84%. In some embodiments, the midsole material has a resilience of 80-83%. In some embodiments, the midsole material has a resilience of 81-82%.

[0041] In some embodiments, the tensile strength of the midsole material is 2.65 to 3.25 MPa. In some embodiments, the tensile strength of the midsole material may be 2.7 to 3.2 MPa. In some embodiments, the tensile strength of the midsole material may be 2.8 to 3.1 MPa. In some embodiments, the tensile strength of the midsole material may be 2.9 to 3.0 MPa.

[0042] In some embodiments, the compression deformation of the midsole material is 27-30%. In some embodiments, the compression deformation of the midsole material can be 28-29%.

[0043] In some embodiments, the delamination tearing resistance of the midsole material is 24-28 N / cm. In some embodiments, the delamination tearing resistance of the midsole material is 25-27 N / cm. In some embodiments, the delamination tearing resistance of the midsole material is 26-27 N / cm.

[0044] In some embodiments, the peak acceleration of the midsole material may be 9.0 to 11.0. In some embodiments, the peak acceleration of the midsole material may be 9.25 to 10.75. In some embodiments, the peak acceleration of the midsole material may be 9.5 to 10.5. In some embodiments, the peak acceleration of the midsole material may be 9.75 to 10.25. In some embodiments, the peak acceleration of the midsole material may be 10.0 to 10.25.

[0045] The experimental methods in the following examples are conventional methods unless otherwise specified. The experimental materials used in the following examples are purchased from conventional biochemical reagent companies unless otherwise specified. The quantitative tests in the following examples are repeated three times, and the results are averaged.

[0046] Sources of main raw materials: PDO (1,3-propylene glycol), PO3G (bio-based poly 1,3-propylene glycol, 2000g / mol), purchased from DuPont. HDI (hexamethylene diisocyanate), PEBA 501 nylon elastomer, TPU A902 aliphatic polyurethane, produced by Wanhua Chemical Group Co., Ltd.; Decanoic acid DC10, dodecanedioic acid DC12, purchased from Shanghai Kaisai Biotechnology Co., Ltd.; IS (isosorbide) purchased from PolyChemical.

[0047] Example 1

[0048] (1) Weigh the following raw materials in the following mass percentages: 47 parts of sebacic acid, 53 parts of 1,3-propylene glycol, 0.01 parts of catalyst butyl tin oxide, and 0.5 parts of antioxidant 1010, and put them into a reaction container. Slowly increase the temperature under argon and stirring conditions, and react at 160-220°C until the acid value of the system is less than 30 mg KOH / g. In the second stage, gradually increase the vacuum degree of the system at 220°C to remove the water generated by the reaction, maintain the vacuum degree at 20-30 Pa, and allow the reaction to continue. When the acid value of the system is less than 1.0 mg KOH / g, the reaction is terminated, and the temperature is lowered to 60-70°C to discharge the material to obtain poly 1,3-propylene sebacic acid ester, and the number average molecular weight thereof is 2200 g / mol as measured by gel permeation chromatography.

[0049] (2) Weigh the raw materials according to the following mass percentages: 40 parts of poly(1,3-propylene glycol sebacate), 20 parts of polytrimethylene ether glycol, 28.4 parts of HDI, 0.6 parts of UV resistant agent 3280, and 0.3 parts of antioxidant 1010. Add poly(1,3-propylene glycol suberate), polypropylene glycol, UV-resistant and antioxidant additives to a preparation kettle, stir at 100°C for 2h to ensure that the additives are fully dissolved or evenly dispersed to obtain a mixture; then transport the mixture and HDI to the pouring port of a twin-screw extruder through a gear pump, mix evenly, the temperature of each zone of the extruder is 120°C for zone 1, 150°C for zone 2, 170°C for zones 3, 4 and 5, 180°C for zones 6, 7 and 8, 190°C for zones 9 and 10, the head temperature is 200°C, the screw speed is 400rpm, 4 parts of nano-talcum powder as a nucleating agent is added to zones 4-6 at the rear end of the reaction zone, and 11.6 parts of PDO as a chain extender is added to zones 5-7 at the rear end of the reaction zone, extruded by reaction, squeezed into a mold, cooled and solidified at room temperature, to obtain a sheet of thermoplastic polyurethane elastomer;

[0050] (3) The method for preparing the thermoplastic polyurethane elastomer midsole is as follows: the polyurethane elastomer sheet is placed in a nitrogen supercritical fluid device and maintained at a pressure of 10 to 40 MPa and a temperature of 100 to 140 degrees Celsius for 3 to 6 hours. The pressure is then released to a pressure of 1 to 3 MPa within 0.5 to 1 hour to obtain the high-elastic shock-absorbing foam material.

[0051] Example 2

[0052] (1) Weigh the following raw materials in the following mass percentages: 46.7 parts of dodecanedioic acid, 53.3 parts of 1,3-propylene glycol, 0.01 parts of catalyst butyl tin oxide, and 0.5 parts of antioxidant 1010, and put them into a reaction container. Slowly increase the temperature under argon and stirring conditions, and react at 160-220°C until the acid value of the system is less than 30 mg KOH / g. In the second stage, gradually increase the vacuum degree of the system at 220°C to remove the water generated by the reaction, maintain the vacuum degree at 20-30 Pa, and allow the reaction to continue. When the acid value of the system is less than 1.0 mg KOH / g, the reaction is terminated, and the temperature is lowered to 60-70°C to discharge the material to obtain poly (1,3-propylene glycol dodecanedioate), and the number average molecular weight thereof is 2000 g / mol as measured by gel permeation chromatography.

[0053] (2) Weigh the raw materials according to the following mass percentages: 40 parts of poly(1,3-propylene glycol dodecanedioate), 20 parts of polytrimethylene ether glycol, 28.4 parts of HDI, 0.6 parts of UV resistant agent 3280, and 0.3 parts of antioxidant 1010. Add poly(1,3-propylene glycol suberate), polypropylene glycol, UV-resistant and antioxidant additives to a preparation kettle, stir at 100°C for 2h to ensure that the additives are fully dissolved or evenly dispersed to obtain a mixture; then transport the mixture and HDI to the pouring port of a twin-screw extruder through a gear pump, mix evenly, the temperature of each zone of the extruder is 120°C for zone 1, 150°C for zone 2, 170°C for zones 3, 4 and 5, 180°C for zones 6, 7 and 8, 190°C for zones 9 and 10, the head temperature is 200°C, the screw speed is 400rpm, 4 parts of nano-talcum powder as a nucleating agent is added to zones 4-6 at the rear end of the reaction zone, and 11.6 parts of PDO as a chain extender is added to zones 5-7 at the rear end of the reaction zone, extruded by reaction, squeezed into a mold, cooled and solidified at room temperature, to obtain a sheet of thermoplastic polyurethane elastomer;

[0054] (3) The method for preparing the thermoplastic polyurethane elastomer midsole is as follows: the polyurethane elastomer sheet is placed in a nitrogen supercritical fluid device and maintained at a pressure of 10 to 40 MPa and a temperature of 100 to 140 degrees Celsius for 3 to 6 hours. The pressure is then released to a pressure of 1 to 3 MPa within 0.5 to 1 hour to obtain the high-elastic shock-absorbing foam material.

[0055] Example 3

[0056] (1) Weigh the following raw materials in the following mass percentages: 46.1 parts of sebacic acid, 53.9 parts of isosorbide, 0.01 parts of catalyst butyl tin oxide, and 0.5 parts of antioxidant 1010, and put them into a reaction container. Slowly increase the temperature under argon and stirring conditions, and react at 160-220°C until the acid value of the system is less than 30 mg KOH / g. In the second stage, gradually increase the vacuum degree of the system at 220°C to remove the water generated by the reaction, maintain the vacuum degree at 20-30 Pa, and allow the reaction to continue. When the acid value of the system is less than 1.0 mg KOH / g, the reaction is terminated, and the temperature is lowered to 60-70°C to discharge the material to obtain polyisosorbide sebacate, and the number average molecular weight thereof is 2150 g / mol as measured by gel permeation chromatography.

[0057] (2) Weigh the raw materials according to the following mass percentages: 35 parts of polyisosorbide sebacate, 35 parts of polytrimethylene ether glycol, 21.7 parts of HDI, 0.6 parts of UV resistant agent 3280, and 0.4 parts of antioxidant 1010. Add poly(1,3-propylene glycol suberate), polypropylene glycol, UV-resistant and antioxidant additives to a preparation kettle, stir at 100°C for 2h to ensure that the additives are fully dissolved or evenly dispersed to obtain a mixture; then transport the mixture and HDI to the pouring port of a twin-screw extruder through a gear pump, mix evenly, the temperature of each zone of the extruder is 120°C for zone 1, 150°C for zone 2, 170°C for zones 3, 4 and 5, 180°C for zones 6, 7 and 8, 190°C for zones 9 and 10, the head temperature is 200°C, the screw speed is 400rpm, 4 parts of nano-talcum powder as a nucleating agent is added to zones 4-6 at the rear end of the reaction zone, and 8.3 parts of chain extender PDO are added to zones 5-7 at the rear end of the reaction zone, extruded through reaction, squeezed into a mold, cooled and solidified at room temperature, to obtain a sheet of thermoplastic polyurethane elastomer;

[0058] (3) The method for preparing the thermoplastic polyurethane elastomer midsole is as follows: the polyurethane elastomer sheet is placed in a nitrogen supercritical fluid device and maintained at a pressure of 10 to 40 MPa and a temperature of 100 to 140 degrees Celsius for 3 to 6 hours. The pressure is then released to a pressure of 1 to 3 MPa within 0.5 to 1 hour to obtain the high-elastic shock-absorbing foam material.

[0059] Example 4

[0060] (1) Weigh the following raw materials in the following mass percentages: 45.8 parts of sebacic acid, 54.2 parts of isosorbide, 0.01 parts of catalyst butyl tin oxide, and 0.5 parts of antioxidant 1010, and put them into a reaction container. Slowly increase the temperature under argon and stirring conditions, and react at 160-220°C until the acid value of the system is less than 30 mg KOH / g. In the second stage, gradually increase the vacuum degree of the system at 220°C to remove the water generated by the reaction, maintain the vacuum degree at 20-30 Pa, and allow the reaction to continue. When the acid value of the system is less than 1.0 mg KOH / g, terminate the reaction, cool to 60-70°C, and discharge the material to obtain polyisosorbide dodecanedioate, and its number average molecular weight is 2300 g / mol as measured by gel permeation chromatography.

[0061] (2) Weigh the raw materials according to the following mass percentages: 35 parts of polyisosorbide dodecanedioate, 35 parts of polytrimethylene ether glycol, 21.7 parts of HDI, 0.6 parts of UV resistant agent 3280, and 0.4 parts of antioxidant 1010. Add poly(1,3-propylene glycol suberate), polypropylene glycol, UV-resistant and antioxidant additives to a preparation kettle, stir at 100°C for 2h to ensure that the additives are fully dissolved or evenly dispersed to obtain a mixture; then transport the mixture and HDI to the pouring port of a twin-screw extruder through a gear pump, mix evenly, the temperature of each zone of the extruder is 120°C for zone 1, 150°C for zone 2, 170°C for zones 3, 4 and 5, 180°C for zones 6, 7 and 8, 190°C for zones 9 and 10, the head temperature is 200°C, the screw speed is 400rpm, 4 parts of nano-talcum powder as a nucleating agent is added to zones 4-6 at the rear end of the reaction zone, and 8.3 parts of chain extender PDO are added to zones 5-7 at the rear end of the reaction zone, extruded through reaction, squeezed into a mold, cooled and solidified at room temperature, to obtain a sheet of thermoplastic polyurethane elastomer;

[0062] (3) The method for preparing the thermoplastic polyurethane elastomer midsole is as follows: the polyurethane elastomer sheet is placed in a nitrogen supercritical fluid for 3 to 6 hours at a pressure of 10 to 40 MPa and a temperature of 100 to 140 degrees Celsius. The pressure is then released to a pressure of 1 to 3 MPa within 0.5 to 1 hour to obtain the high-elastic shock-absorbing foam material.

[0063] Comparative Example 1

[0064] (1) an aliphatic elastomer (brand A190, Meirui New Materials) is placed in an oven for drying, and a mixture of 100 parts of the polyurethane elastomer, 0.3 parts of an antioxidant 1010, and 4 parts of a nucleating agent nano-talc powder is placed in a high-speed mixer for stirring, and after stirring evenly, a thermoplastic polyurethane elastomer sheet is obtained by extruding the mixture into a die through a twin-screw extruder;

[0065] (2) placing the polyurethane elastomer sheet in a nitrogen supercritical fluid device and maintaining the pressure for 3 to 6 hours at a pressure of 10 to 40 MPa and a temperature of 100 to 140 degrees Celsius, and releasing the pressure to a pressure of 1 to 3 MPa within 0.5 to 1 hour to obtain the high-elastic shock-absorbing foam material.

[0066] Comparative Example 2

[0067] (1) placing an aliphatic polyurethane elastomer (brand name WHT A902, Wanhua) in an oven for drying, and placing a mixture of 100 parts of the polyurethane elastomer, 0.3 parts of an antioxidant 1010, and 4 parts of a nucleating agent nano talc in a high-speed mixer for stirring, and after stirring evenly, passing through a twin-screw extrusion die to obtain a thermoplastic polyurethane elastomer sheet;

[0068] (2) placing the polyurethane elastomer sheet in a nitrogen supercritical fluid device and maintaining the pressure for 3 to 6 hours at a pressure of 10 to 40 MPa and a temperature of 100 to 140 degrees Celsius, and releasing the pressure to a pressure of 1 to 3 MPa within 0.5 to 1 hour to obtain the high-elastic shock-absorbing foam material.

[0069] Comparative Example 3

[0070] (1) placing an aliphatic polyurethane elastomer (brand number 85085A, Covestro) in an oven for drying, and placing a mixture of 100 parts of the polyurethane elastomer, 0.3 parts of an antioxidant 1010, and 4 parts of a nucleating agent nano talc in a high-speed mixer for stirring, and after stirring evenly, passing through a twin-screw extrusion die to obtain a thermoplastic polyurethane elastomer sheet;

[0071] (2) placing the polyurethane elastomer sheet in a nitrogen supercritical fluid device and maintaining the pressure for 3 to 6 hours at a pressure of 10 to 40 MPa and a temperature of 100 to 140 degrees Celsius, and releasing the pressure to a pressure of 1 to 3 MPa within 0.5 to 1 hour to obtain the high-elastic shock-absorbing foam material.

[0072] The thermoplastic polyurethane materials provided in Examples 1-4 and Comparative Examples 1-3 were subjected to various performance tests shown in Table 1 according to the following methods. The results are shown in Table 1 below:

[0073] Table 1

[0074]

[0075] It can be seen from Example 1, Example 2, Example 3, Example 4 and Comparative Example 1, Comparative Example 2, and Comparative Example 3 that the long fatty chain bio-based aliphatic polyurethane foamed shoe material has a density of 0.08 to 0.11 g / cm 3, hardness of 35-39C, resilience greater than 79%, peak acceleration (Peak G) 9-11; basically comparable to the physical properties of the mainstream aliphatic TPU, TPEE and PEBA sole materials in the current market. The polyurethane foam material prepared based on bio-based 1,3-propylene glycol is similar to the mainstream structure in the market, but the material properties are more outstanding based on the flexibility and crystallinity of the long chain segment. The polyurethane foam material prepared based on isosorbide has stronger material toughness due to the rigid unit of the subject unit and the linear segments of polyester and polyether. The invention patent proposes a bio-based long-chain aliphatic polyurethane elastomer and a method for preparing a midsole material, which can bring beneficial effects including but not limited to: (1) More than 50% of the synthetic raw materials are biomass raw materials, which has good sustainability and environmental protection, and the formula ingredients are simple and have the potential for recycling. (2) Compared with the high-end midsole materials in the market, the midsole material has better rebound and lower compression deformation, and the cost of the raw materials will be lower than that of PEBAX raw materials, which broadens the selection range of raw materials for high-performance physical foaming and can be applied to the midsoles of high-end sports shoes. (3) The polyurethane elastic material has the potential for other high mechanical engineering applications.

[0076] The basic concepts have been described above. Obviously, for those skilled in the art, the above detailed disclosure is only for example and does not constitute a limitation of this specification. Although not explicitly stated here, those skilled in the art may make various modifications, improvements and corrections to this specification. Such modifications, improvements and corrections are suggested in this specification, so such modifications, improvements and corrections still belong to the spirit and scope of the exemplary embodiments of this specification.

[0077] At the same time, this specification uses specific words to describe the embodiments of this specification. For example, "one embodiment", "an embodiment", and / or "some embodiments" refer to a certain feature, structure or characteristic related to at least one embodiment of this specification. Therefore, it should be emphasized and noted that "one embodiment" or "an embodiment" or "an alternative embodiment" mentioned twice or more in different positions in this specification does not necessarily refer to the same embodiment. In addition, certain features, structures or characteristics in one or more embodiments of this specification can be appropriately combined.

[0078] In some embodiments, numbers describing the number of components and attributes are used. It should be understood that such numbers used in the description of the embodiments are modified by the modifiers "about", "approximately" or "substantially" in some examples. Unless otherwise specified, "about", "approximately" or "substantially" indicate that the numbers are allowed to vary by ±20%. Accordingly, in some embodiments, the numerical parameters used in the specification and claims are approximate values, which may change according to the required features of individual embodiments. In some embodiments, the numerical parameters should take into account the specified significant digits and adopt the general method of retaining digits. Although the numerical domains and parameters used to confirm the breadth of their range in some embodiments of this specification are approximate values, in specific embodiments, the setting of such numerical values ​​is as accurate as possible within the feasible range.

[0079] Finally, it should be understood that the embodiments described in this specification are only used to illustrate the principles of the embodiments of this specification. Other variations may also fall within the scope of this specification. Therefore, as an example and not a limitation, alternative configurations of the embodiments of this specification may be considered consistent with the teachings of this specification. Accordingly, the embodiments of this specification are not limited to the embodiments explicitly introduced and described in this specification.

Claims

1. A thermoplastic polyurethane elastomer, characterized in that: The invention comprises the following raw materials in parts by weight: 30-45 parts of polyester polyol, 15-40 parts of polyether polyol, 0.4-0.8 parts of UV resistance agent, 0.2-0.5 parts of antioxidant, 20-30 parts of isocyanate, 3-5 parts of nucleating agent and 8-12 parts of chain extender.

2. The elastic body according to claim 1, characterized in that The invention comprises the following raw materials in parts by weight: 35-40 parts of polyester polyol, 20-35 parts of polyether polyol, 0.5-0.7 parts of UV resistance agent, 0.3-0.4 parts of antioxidant, 21.7-28.4 parts of isocyanate, 3-5 parts of nucleating agent and 8-12 parts of chain extender.

3. The elastic body according to claim 1 or 2, characterized in that: The number average molecular weight of the polyester polyol is 800 to 3000 g / mol; And / or, the polyester polyol is selected from one or more of poly(1,3-propylene adipate), poly(1,3-propylene suberate), poly(1,3-propylene sebacate), poly(1,3-propylene dodecanedioate), poly(isosorbide adipate), poly(isosorbide suberate), poly(isosorbide sebacate) or poly(isosorbide dodecanedioate); and / or, the number average molecular weight of the polyether polyol is 500 to 2000 g / mol, And / or, the polyether polyol is selected from one or more of polytrimethylene ether glycol, polytetramethylene ether glycol, tetramethylene oxide copolymer glycol or polypropylene glycol, polyoxypropylene glycol or polyoxypropylene triol; And / or, the UV-resistant agent is selected from UV-resistant agent 3280, titanium oxide, carbon black pigment, tetrakis(methylene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid)methane or One or more of PU836; and / or, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1098 and antioxidant 1076; and / or, the isocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or 1,5-pentane diisocyanate; And / or, the nucleating agent is selected from one or more of nano silicon dioxide, nano titanium dioxide, nano calcium carbonate, nano talc or nano zinc oxide; And / or, the chain extender is an alcohol chain extender.

4. The method for preparing the elastomer according to any one of claims 1 to 3, comprising the following steps: (1) Weighing polyester polyol, polyether polyol, UV resistant agent and antioxidant according to weight, mixing and dissolving to prepare a primary mixture; (2) Weighing isocyanate, nucleating agent and chain extender, adding to the primary mixture, stirring evenly, and melt extruding to obtain a thermoplastic polyurethane elastomer.

5. The preparation method according to claim 4, characterized in that: In the step 1), the polyester polyol comprises the following raw materials in parts by weight: 45-50 parts of dibasic acid, 50-55 parts of diol, 0.005-0.015 parts of catalyst and 0.25-0.75 parts of antioxidant. Preferably, the polyester polyol comprises the following raw materials in parts by weight: 45.8-47 parts of dibasic acid, 53-54.2 parts of diol, 0.008-0.012 parts of catalyst and 0.4-0.6 parts of antioxidant. More preferably, the dibasic acid is selected from butanediol. The dibasic acid is selected from one or more of adipic acid, adipic acid, sebacic acid, suberic acid or dodecanedioic acid, the diol is selected from one or more of 1,3-propylene glycol, 1,4-butylene glycol, isosorbide or neopentyl glycol, the catalyst is a tin catalyst, and the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1098 or antioxidant 1076; further preferably, the dibasic acid is selected from sebacic acid or dodecanedioic acid, and the diol is selected from 1,3-propylene glycol or isosorbide; And / or, in the step 2), the isocyanate and the primary mixed material are first transported to the pouring port of a twin-screw extruder, mixed evenly, and then extruded using a twin-screw extruder, extruded into a mold, and cured to obtain a thermoplastic polyurethane elastomer.

6. The preparation method according to claim 5, characterized in that: The temperature of each reaction zone of the extruder is 110-130°C in zone 1, 140-160°C in zone 2, 160-180°C in zones 3, 4 and 5, 170-190°C in zones 6, 7 and 8, 180-200°C in zones 9 and 10, and the die head temperature is 190-210°C. Preferably, a nucleating agent is added in reaction zones 4 to 6, and a chain extender is added in reaction zones 5 to 7; And / or, the screw speed of the twin-screw extruder is 300-500 rpm; And / or, the curing is performed by cooling at room temperature.

7. A method for preparing a thermoplastic polyurethane elastomer midsole material, which is prepared by using the thermoplastic polyurethane elastomer according to any one of claims 1 to 3.

8. The preparation method according to claim 7, characterized in that: The thermoplastic polyurethane elastomer according to any one of claims 1 to 3 is placed in a nitrogen supercritical fluid device to maintain pressure, and then internally discharged to obtain the high-elastic shock-absorbing foam material; preferably, the pressure-maintaining time is 3 to 6 hours; And / or, preferably, the holding pressure is 10-40 MPa; And / or, preferably, the holding temperature is 100-140°C; And / or, preferably, the pressure relief time is 0.5 to 1 hour; And / or, preferably, the pressure is released to a pressure of 1 to 3 MPa.

9. A thermoplastic polyurethane elastomer midsole material prepared by the preparation method according to claim 7 or 8.

10. The thermoplastic polyurethane elastomer midsole material according to claim 9, characterized in that: The hardness of the midsole material is 35 to 39 degrees; And / or, the density of the midsole material is 0.08-0.11 g / cm 3 ; and / or, the resilience of the midsole material is 79-84%; and / or, the tensile strength of the midsole material is 2.65 to 3.25 MPa; and / or, the compression deformation of the midsole material is 27-30%; and / or, the delamination tearing of the midsole material is 24-28 N / cm; And / or, the peak acceleration of the midsole material is 9.0-11.0.

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