High-wear-resistance high-slip-resistance TPU basketball shoe sole sheet containing bio-based component and preparation method therefor

Abstract

A high-wear-resistance high-slip-resistance TPU basketball shoe sole sheet containing a bio-based component and a preparation method therefor. The high-wear-resistance high-slip-resistance TPU basketball shoe sole sheet comprises a plane structure in the middle of a basketball shoe sole and a protruding edge cover structure. The basketball shoe sole specifically comprises the following raw materials: a modified TPU-polyurethane composite material, a stabilizer, an additive, an adhesive film, and a bio-based component. By adding a modified carbon nanotube silicon dioxide-iron dioxide nanomaterial to a TPU-polyurethane composite material for modification, the wear resistance of the prepared basketball shoe sole sheet is improved, and the slip resistance thereof is further improved, so that the surface of the modified TPU-polyurethane composite material has a protrusion-like structure, thereby enhancing the grip force of the material and thus improving the slip-resistance in wet conditions.

Description

A high-wear-resistant and high-anti-slip TPU basketball shoe sole containing bio-based components and a preparation method thereof Technical Field

[0001] The present invention relates to the technical field of TPU basketball shoe soles, in particular to a highly wear-resistant and highly anti-slip TPU basketball shoe sole containing bio-based components and a preparation method thereof. Background Art

[0002] Thermoplastic polyurethane elastomer, also known as thermoplastic polyurethane elastomer, referred to as TPU, is a (AB) n A segmented linear block polymer, A is a high molecular weight (1000-6000) polyester or polyether, B is a diol with 2-12 linear carbon atoms, and the chemical structure between the A and B segments is diisocyanate. Thermoplastic polyurethanes, like adhesives, are crosslinked by intermolecular hydrogen bonds or by light crosslinking between macromolecular chains. Both crosslinking structures are reversible with increasing or decreasing temperature. In the molten state or solution, intermolecular forces weaken, but upon cooling or solvent evaporation, strong intermolecular forces re-establish the bonds, restoring the original solid properties.

[0003] Referring to a Chinese patent for a manufacturing process for a foamed TPU sole (Announcement No.: CN104441409A), the process includes the following steps: mixing TPU particles and a foaming agent through an extruder to form a melt, which is injected into a first sole mold. After the melt injection is completed, the first sole mold is kept warm for 3 to 5 minutes and then cooled to room temperature; the first sole mold is demoulded to obtain a foamed TPU sole. The weight percentage of TPU particles and foaming agent is 100:(1-10); the injection speed of the melt is 50-60 mm / s, and the injection pressure is 10 MPa-15 MPa; the temperature of the first sole mold is maintained at 120-130°C during the melt injection process; the present invention injects a mixture of TPU particles and foaming agent into the first sole mold at a specific injection speed and injection pressure through an extruder, so that the mixture is foamed in the first sole mold to obtain a foamed TPU sole. The foamed TPU sole thus obtained not only maintains the advantages of high hardness of TPU material, but also has light weight and good shock absorption performance due to the micropores of TPU. However, in the above technical solution, the foamed TPU sole prepared has weak anti-slip performance. Therefore, the present invention proposes a high-wear-resistant and high-anti-slip TPU basketball shoe sole containing bio-based components and a preparation method thereof to solve the above-mentioned problems. Summary of the Invention

[0004] (1) Technical problems solved

[0005] In response to the deficiencies in the prior art, the present invention provides a highly wear-resistant and anti-slip TPU basketball shoe sole containing bio-based components and a preparation method thereof, which solves the problems mentioned in the above background technology.

[0006] (2) Technical solution

[0007] To achieve the above objectives, the present invention is implemented through the following technical solutions: a highly wear-resistant and high-slip TPU basketball shoe sole containing bio-based components, including a mid-plane structure of the basketball shoe sole and a raised edge binding structure;

[0008] The basketball shoe sole specifically includes the following raw materials: modified TPU-polyurethane composite material, stabilizer, additive, adhesive film and bio-based.

[0009] Preferably, the edge binding structure has a thickness of 1.0 to 1.5 mm.

[0010] Preferably, the basketball shoe sole specifically comprises the following raw materials in parts by weight: 35-55 parts of modified TPU-polyurethane composite material, 3-6 parts of stabilizer, 20-35 parts of additive, 2-5 parts of adhesive film, and 8-12 parts of bio-based.

[0011] Preferably, the bio-based material is one or a mixture of more than one of corn straw, industrial corn, SPN 9582, and injection molding grade bio-based materials.

[0012] Preferably, the specific preparation steps of the modified TPU-polyurethane composite material are:

[0013] (1) Take the modified carbon nanotube silicon dioxide-iron dioxide nanomaterial and add it into a mixer;

[0014] (2) then adding DMF solution and polyether thermoplastic polyurethane elastomer TPU;

[0015] (3) After ultrasonic dispersion of the mixture in the reactor, the temperature was raised to 75-80°C and stirred for 4-6 hours;

[0016] (4) Finally, the composite material prepared above was placed in an environment of 80-90°C and decompressed to remove the DMF solvent, thereby obtaining a modified TPU-polyurethane composite material.

[0017] Preferably, the stabilizer is azodicarbonamide or sodium bicarbonate, the additive is active zinc oxide, and the adhesive film is an EVA adhesive film.

[0018] A method for preparing a high-wear-resistant and high-slip TPU basketball shoe sole containing bio-based components specifically comprises the following steps:

[0019] S1. Weigh each component in proportion and set aside;

[0020] S2, pouring the modified TPU-polyurethane composite material and additives into a blender;

[0021] S3, add stabilizer and continue stirring until the mixture is evenly mixed;

[0022] S4, finally dehumidification and drying, melt blending and extrusion, salivation, cooling, and trimming to produce the TPU basketball shoe sole.

[0023] Preferably, the mixing time in step S2 is 20 to 30 minutes, and the mixing speed is 180 to 200 r / min.

[0024] Preferably, the mixing time in step S3 is 15 to 20 minutes, and the mixing speed is 260 to 300 r / min.

[0025] Preferably, the dehumidification and drying process in step S4 is carried out in a dehumidification dryer, wherein the dehumidification and drying temperature is 75-95°C and the dehumidification and drying time is 2.5-4h; the melt blending is carried out in a casting machine, and the melt blending temperature is 120-180°C.

[0026] (3) Beneficial effects

[0027] The present invention provides a highly wear-resistant and slip-resistant TPU basketball shoe sole containing bio-based components and a method for preparing the same. Compared to existing technologies, this invention offers the following advantages: the prepared TPU basketball shoe sole is not only environmentally friendly, biodegradable, renewable, and recyclable, but also exhibits better wear resistance than rubber. By adding modified carbon nanotube-silicon dioxide-iron dioxide nanomaterials to the TPU-polyurethane composite material, the sole is modified, improving both its wear resistance and its slip resistance. The surface of the modified TPU-polyurethane composite material has a convex-like structure, which enhances the material's grip and improves its wet-slip resistance. Furthermore, compared to existing technologies, this invention achieves a 33% to 42% improvement in DIN abrasion resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG1 is a Fourier transform infrared spectrum of a modified TPU-polyurethane composite material provided by a high-wear-resistant and high-anti-slip TPU basketball shoe sole containing bio-based components and a preparation method thereof according to the present invention;

[0029] FIG2 is a scanning electron microscope image of the surface of a basketball shoe sole provided by a high-wear-resistant and high-anti-slip TPU basketball shoe sole containing bio-based components and a preparation method thereof according to the present invention;

[0030] FIG3 is a TEM image of a basketball shoe sole provided by a high-wear-resistant and high-anti-slip TPU basketball shoe sole containing bio-based components and a preparation method thereof according to the present invention. DETAILED DESCRIPTION

[0031] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0032] In this technical solution, the main component of the DMF solution is NN-dimethylformamide.

[0033] The embodiments of the present invention provide the following technical solutions:

[0034] Example 1

[0035] A highly wear-resistant and anti-slip TPU basketball shoe sole containing bio-based components, comprising a mid-plane structure of the basketball shoe sole and a raised edge edging structure; the edge edging structure has a thickness of 1.0 mm;

[0036] Among them, the basketball shoe sole specifically includes the following raw materials: 35 parts of modified TPU-polyurethane composite material, 3 parts of stabilizer, 20 parts of additives, 5 parts of film, and 12 parts of bio-based materials, among which the bio-based materials are 10 parts of corn straw and 2 parts of industrial corn.

[0037] In the embodiment of the present invention, the specific preparation steps of the modified TPU-polyurethane composite material are:

[0038] (1) Take the modified carbon nanotube silicon dioxide-iron dioxide nanomaterial and add it into a mixer;

[0039] (2) then adding DMF solution and polyether thermoplastic polyurethane elastomer TPU;

[0040] (3) After ultrasonic dispersion of the mixture in the reactor, the temperature was raised to 75°C and stirred for 4 hours;

[0041] (4) Finally, the composite material prepared above was placed in an environment of 80°C and decompressed to remove the DMF solvent, thereby obtaining a modified TPU-polyurethane composite material.

[0042] A method for preparing a high-wear-resistant and high-slip TPU basketball shoe sole containing bio-based components specifically comprises the following steps:

[0043] S1. Weigh each component in proportion and set aside;

[0044] S2, pouring the modified TPU-polyurethane composite material and activated zinc oxide into a blender, mixing for 20 minutes at a mixing speed of 200 r / min;

[0045] S3, then add azodicarbonamide and bio-based, continue stirring until mixed evenly, the mixing time is 150 minutes, and the mixing speed is 300r / min;

[0046] S4. Finally, the product is dehumidified and dried in a dehumidifying dryer at a temperature of 75° C. for 2.5 hours. The product is melt-blended and extruded in a casting machine at a temperature of 120° C., followed by salivation, cooling, and trimming to produce a TPU basketball shoe sole.

[0047] Example 2

[0048] A highly wear-resistant and slip-resistant TPU basketball shoe sole containing bio-based components, comprising a mid-plane structure and a raised edge edging structure; the edge edging structure has a thickness of 1.3 mm;

[0049] Among them, the basketball shoe sole specifically includes the following raw materials: 45 parts of modified TPU-polyurethane composite material, 5 parts of stabilizer, 30 parts of additives, 5 parts of adhesive film, and 10 parts of bio-based. Among them, the bio-based material is SPN 9582 produced by DuPont, and its formula contains bio-based polyols and bio-based BDO, which are sourced from sugarcane.

[0050] In the embodiment of the present invention, the specific preparation steps of the modified TPU-polyurethane composite material are:

[0051] (1) Take the modified carbon nanotube silicon dioxide-iron dioxide nanomaterial and add it into a mixer;

[0052] (2) then adding DMF solution and polyether thermoplastic polyurethane elastomer TPU;

[0053] (3) After ultrasonic dispersion of the mixture in the reactor, the temperature was raised to 78°C and stirred for 5 hours;

[0054] (4) Finally, the composite material prepared above was placed in an environment of 85°C and decompressed to remove the DMF solvent, thereby obtaining a modified TPU-polyurethane composite material.

[0055] A method for preparing a high-wear-resistant and high-slip TPU basketball shoe sole containing bio-based components specifically comprises the following steps:

[0056] S1. Weigh each component in proportion and set aside;

[0057] S2, pouring the modified TPU-polyurethane composite material and active zinc oxide into a blender, mixing for 25 minutes at a mixing speed of 190 r / min;

[0058] S3. Add sodium bicarbonate and bio-based materials and continue stirring until the mixture is evenly mixed. The mixing time is 17 minutes and the mixing speed is 280 r / min.

[0059] S4. Finally, the product is dehumidified and dried in a dehumidifying dryer at a temperature of 85° C. for 3.5 hours. The product is melt-blended and extruded in a casting machine at a temperature of 150° C., followed by salivation, cooling, and trimming to produce a TPU basketball shoe sole.

[0060] Example 3

[0061] A highly wear-resistant and slip-resistant TPU basketball shoe sole containing bio-based components, comprising a mid-plane structure and a raised edge edging structure; the edge edging structure has a thickness of 1.5 mm;

[0062] Among them, the basketball shoe sole specifically includes the following raw materials: 55 parts of modified TPU-polyurethane composite material, 3 parts of stabilizer, 35 parts of additives, 4 parts of film, and 8 parts of bio-based. Among them, the bio-based material is injection-molding grade bio-based TPU. Depending on the brand, its sources include corn starch, castor oil, etc.

[0063] In the embodiment of the present invention, the specific preparation steps of the modified TPU-polyurethane composite material are:

[0064] (1) Take the modified carbon nanotube silicon dioxide-iron dioxide nanomaterial and add it into a mixer;

[0065] (2) then adding DMF solution and polyether thermoplastic polyurethane elastomer TPU;

[0066] (3) After ultrasonic dispersion of the mixture in the reactor, the temperature was raised to 80°C and stirred for 6 hours;

[0067] (4) Finally, the composite material prepared above was placed in an environment of 90°C and decompressed to remove the DMF solvent, thereby obtaining a modified TPU-polyurethane composite material.

[0068] A method for preparing a high-wear-resistant and high-slip TPU basketball shoe sole containing bio-based components specifically comprises the following steps:

[0069] S1. Weigh each component in proportion and set aside;

[0070] S2, pouring the modified TPU-polyurethane composite material and active zinc oxide into a blender, mixing for 30 minutes at a mixing speed of 180 r / min;

[0071] S3, then add azodicarbonamide and bio-based, continue stirring until mixed evenly, the mixing time is 20 minutes, and the mixing speed is 260r / min;

[0072] S4. Finally, the product is dehumidified and dried in a dehumidifying dryer at a temperature of 95° C. for 4 hours. The product is melt-blended and extruded in a casting machine at a temperature of 180° C., followed by salivation, cooling, and trimming to produce a TPU basketball shoe sole.

[0073] Comparative Example 1

[0074] S1. Weigh each component in proportion and set aside, including 35 parts of TPU material, 3 parts of stabilizer, 20 parts of additives, and 5 parts of film;

[0075] S2. Pour the TPU material and activated zinc oxide into a blender, mix for 20 minutes, and mix at a speed of 200 r / min;

[0076] S3, then add azodicarbonamide, continue stirring until mixed evenly, the mixing time is 150 minutes, and the mixing speed is 300r / min;

[0077] S4. Finally, the product is dehumidified and dried in a dehumidifying dryer at a temperature of 70° C. for 3 hours. The product is melt-blended and extruded in a casting machine at a temperature of 100° C., and the product is drooled, cooled, and trimmed to produce a TPU basketball shoe sole.

[0078] Wear resistance test: The finished shoe sample is balanced in a laboratory environment for more than 8 hours. Based on the size of the finished shoe sample, a suitable standard head (generally 0.5-1 size smaller than the sample size) is selected and inserted into the finished shoe sample, ensuring that there is no slippage between the head and the finished shoe sample. The total mass of the finished shoe sample and the head is weighed (W1). The bottom of the finished shoe sample and the glass plate are cleaned with a 50% alcohol solution and then naturally dried. The finished shoe slip tester is turned on and the pressure is adjusted to 5kg / cm 2; Start the PUMP button to raise the fixture seat, correctly install the finished shoe sample and head under the fixture, and lock it with the fixing screws; start the PUMP button to lower the fixture seat, and the finished shoe sample and test bench are in close contact. Loosen the screws on both sides of the fixture seat, adjust the position of the fixture up and down and left and right, so that the sole of the finished shoe sample is in close contact and parallel to the test bench, ensure that the pitch angle of the finished shoe is 0 degrees (that is, the friction angle of the finished shoe is 0 degrees), then lock the screws 7 on both sides of the fixture seat and start the PUMP button to raise the fixture seat and install the test ground (glass plate) on the test bench; take a 25kg weight and place it on the loading device; open the software program, select the finished shoe anti-slip test, set the speed to 100mm / min and the stroke to 100mm, 5 times, start the test switch to start the test; record the average friction force each time, and calculate the friction coefficient according to the formula; measure at least 5 data for each sample, and take the arithmetic mean of the middle 3 similar data as the final measurement result (the deviation between each data and its arithmetic mean shall not exceed 5%, otherwise multiple data shall be measured); calculate the dry friction coefficient according to the formula (the result is rounded to 2 decimal places). The results are shown in Table 1:

[0079] Table 1

[0080] Meanwhile, the contents not described in detail in this specification belong to the prior art known to those skilled in the art.

[0081] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0082] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A high-wear-resistant and high-slip-resistant TPU basketball sole sheet containing bio-based components, characterized in that: It includes the middle plane structure of the basketball shoe sole and the raised edge wrapping structure; Among them, the basketball shoe sole specifically includes the following raw materials: Modified TPU-polyurethane composite material, stabilizer, additive, adhesive film and bio-based material.

2. The high-wear-resistant and high-slip-resistant TPU basketball sole sheet containing bio-based components according to claim 1, wherein: The thickness of the edge wrapping structure is 1.0 - 1.5 mm.

3. A highly wear-resistant and high anti-slip TPU basketball sole sheet containing bio-based components according to claim 1, characterized in that: The basketball shoe sole specifically includes the following raw materials in parts by weight: 35 - 55 parts of modified TPU-polyurethane composite material, 3 - 6 parts of stabilizer, 20 - 35 parts of additive, 2 - 5 parts of adhesive film, and 8 - 12 parts of bio-based material.

4. A highly wear-resistant and non-slip TPU basketball sole sheet containing bio-based components according to claim 1, characterized in that: The bio-based material is one or more mixtures of corn straw and industrial corn, SPN 9582, and injection-grade bio-based material.

5. A high-wear-resistant and high-slip-resistant TPU basketball sole sheet containing bio-based components according to claim 1, characterized in that: The specific preparation steps of the modified TPU-polyurethane composite material are as follows: (1). Take the modified carbon nanotube silica-iron dioxide nanomaterial and add it to a mixer; (2). Then add DMF solution and polyether-type thermoplastic polyurethane elastomer TPU; (3). After ultrasonic dispersion of the mixture in the reactor, heat it up to 75 - 80 °C and stir for 4 - 6 hours; (4). Finally, place the above-prepared composite material under reduced pressure in an environment of 80 - 90 °C to remove the DMF solvent, and the modified TPU-polyurethane composite material is obtained.

6. A highly wear-resistant and high anti-slip TPU basketball sole sheet containing bio-based components according to claim 1, characterized in that: The stabilizer is azodicarbonamide or sodium bicarbonate, the additive is active zinc oxide, and the adhesive film is an EVA adhesive film.

7. A method for preparing a highly wear-resistant and high anti-slip TPU basketball sole sheet containing bio-based components according to claim 1, characterized in that, Specifically, it includes the following steps: S1. Weigh each component according to the proportion and set aside; S2. Pour the modified TPU-polyurethane composite material and the additive into a blender; S3. Then add the stabilizer and continue to stir until evenly mixed; S4. Finally, carry out dehumidifying and drying, melt blending and extrusion, casting, cooling, and trimming to make a TPU basketball shoe sole sheet.

8. The preparation method of a highly wear-resistant and high anti-slip TPU basketball sole sheet containing bio-based components according to claim 7, characterized in that: The mixing time in step S2 is 20 - 30 minutes, and the mixing speed is 180 - 200 r / min.

9. The preparation method of a highly wear-resistant and high anti-slip TPU basketball sole sheet containing a bio-based component according to claim 7, characterized in that: The mixing time in step S3 is 15 - 20 minutes, and the mixing speed is 260 - 300 r / min.

10. The preparation method of a highly wear-resistant and highly anti-slip TPU basketball sole sheet containing a bio-based component according to claim 7, characterized in that: The dehumidifying and drying process in step S4 is carried out in a dehumidifying dryer, where the dehumidifying and drying temperature is 75 - 95 °C, and the dehumidifying and drying time is 2.5 - 4 h; the melt blending is carried out in a casting machine, and the melt blending temperature is 120 - 180 °C.

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