A kind of thermoplastic elastomer shoe material and preparation method thereof

Abstract

The present invention relates to the technical field of preparation of thermoplastic elastomer shoe materials, and in particular to a thermoplastic elastomer shoe material and a preparation method thereof. The present application provides a thermoplastic elastomer shoe material, including the following weight parts of materials: 20-30 parts of EVA resin, 3-8 parts of foaming agent, 0.1-1.0 parts of antioxidant, 1-5 parts of compatibilizer, 1-5 parts of zinc stearate and 3-8 parts of modified resin particles; the modified resin particles are thermoplastic polyamide elastomers, and the polyamide elastomers include at least one of polyether block amide, polyether ester amide and polyester amide. The present application combines the excellent mechanical properties of thermoplastic polyamide elastomers with the flexibility of EVA, and can effectively disperse and absorb the external pressure and impact force applied to the material, reducing the wear caused by friction. The tear resistance and impact resistance of the shoe material are enhanced, so that the EVA material shows excellent wear resistance and mechanical properties in practical applications.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of thermoplastic elastomer shoe materials, in particular to a thermoplastic elastomer shoe material and a preparation method thereof. Background Art

[0002] Thermoplastic elastomer is a material that has both plastic and rubber properties and has been widely used in the field of footwear in recent years. Thermoplastic elastomers are composed of polymer chains that can soften when heated and return to their original shape after cooling, with excellent resilience and toughness. This allows it to provide excellent comfort and durability when manufacturing footwear, especially for sports shoes, casual shoes and functional shoes. Compared with traditional rubber and foam materials, thermoplastic elastomers are more flexible in the processing process and can be formed by injection molding, extrusion and other methods, reducing production costs. In addition, the environmental performance of thermoplastic elastomers has gradually received attention, and many thermoplastic elastomer materials can be recycled and reused, which is in line with the trend of sustainable development.

[0003] EVA is an important thermoplastic elastomer, which is widely used in various fields due to its excellent physical and chemical properties, especially in the footwear industry. EVA has good wear resistance, elasticity and toughness, and has a low density, making the footwear light and comfortable. Its unique foaming properties also enable EVA to provide excellent shock absorption effect, reducing the impact on the feet during exercise. Compared with traditional materials, EVA is more flexible in processing and can present different forms through various processes such as injection molding, extrusion and foaming to meet different design requirements. In addition, EVA is non-toxic, odorless, meets environmental protection requirements, and is suitable for products with high safety requirements such as children's and sports shoes.

[0004] According to the above-mentioned related technologies, the existing EVA thermoplastic elastomer shoe material is easy to wear under high-intensity use due to its relatively soft molecular structure. In particular, the wear rate of the sole will be accelerated when walking on rough or uneven ground. In addition, EVA is prone to aging, cracking and deformation during long-term use, further reducing the durability of the sole. Summary of the invention

[0005] In order to improve the defects of the existing EVA thermoplastic elastomer shoe material in terms of poor wear resistance and durability, the present application provides a thermoplastic elastomer shoe material and a preparation method thereof.

[0006] In a first aspect, the present application provides a thermoplastic elastomer shoe material, which adopts the following technical solution:

[0007] A thermoplastic elastomer shoe material, characterized by comprising the following materials in parts by weight:

[0008] 20-30 parts of EVA resin;

[0009] 3-8 parts of foaming agent;

[0010] Antioxidant 0.1-1.0 part;

[0011] 1-5 parts of compatibilizer;

[0012] 1-5 parts of zinc stearate;

[0013] 3-8 parts of modified resin particles;

[0014] The modified resin particles are thermoplastic polyamide elastomers, and the polyamide elastomers include at least one of polyether block amide, polyether ester amide and polyester amide.

[0015] Through the above technical scheme, the present application combines the excellent mechanical properties of thermoplastic polyamide elastomer with the flexibility of EVA. Since the molecular structure of thermoplastic polyamide elastomer has high strength and toughness, it can effectively disperse and absorb the external pressure and impact force applied to the material, reducing the wear caused by friction. In addition, the heat resistance and chemical resistance of thermoplastic polyamide elastomer make the material stable under high temperature and harsh environment, not easy to age and deform, thereby extending the service life. The present application optimizes the composition ratio of thermoplastic polyamide elastomer and EVA to form a uniform interlaced network structure, enhances the tear resistance and impact resistance of the shoe material, and makes the modified EVA material show excellent wear resistance and mechanical properties in practical applications.

[0016] Furthermore, the thermoplastic elastomer shoe material also includes 0.5-3.0 parts of porous inorganic modified particles.

[0017] Through the above technical solution, the present application uses porous inorganic modified particles for modification. On the one hand, the structure of the porous inorganic modified particles can reduce the overall weight of the material, while increasing the shock absorption and support performance of the sole. On the other hand, the porous inorganic modified particles have good roughness and friction resistance, thereby further improving the wear resistance of the thermoplastic elastomer shoe material.

[0018] Furthermore, the porous inorganic modified particles are foamed ceramic particles, and the foamed ceramic particles are zirconia foamed ceramic particles.

[0019] Furthermore, the zirconia foam ceramic particles are made by the following technical solution:

[0020] Zirconium oxychloride is placed in ethanol and stirred, yttrium nitrate and nitric acid are added and mixed, after flocculent precipitation occurs, formamide and polyethylene glycol are added and stirred, and a mixed solution is collected;

[0021] The mixed solution is mixed with propylene oxide and stirred and allowed to stand for aging, and the sol solution is collected and washed and dried to obtain an aerogel;

[0022] The aerogel is mixed with zirconium oxychloride and deionized water is added, and the slurry is collected by stirring. The slurry is mixed with a polyethylene glycol / hydrogen peroxide solution and placed in a mold. The mixture is dried and transferred to a calcining furnace. After sintering, the mixture is allowed to stand and cool to room temperature, and then the mixture is crushed, ground and sieved to prepare zirconium oxide foam ceramic particles.

[0023] Through the above technical solution, the present application selects zirconium oxide foam ceramic particles as porous inorganic modified particles, which have significant wear resistance and impact resistance. The lightweight characteristics of zirconium oxide foam ceramic particles are combined with durability, so that the sole can withstand greater pressure and impact while maintaining lightness.

[0024] Based on the above scheme, the present application makes the final product have good mechanical properties and thermal stability through the mixed reaction of zirconium oxychloride and ethanol, combined with the subsequent aging and calcination steps. This technical solution makes the manufacturing process highly controllable, and the particles finally obtained can effectively improve the comprehensive performance of the shoe material, especially in terms of wear resistance and impact resistance, ensuring the long-term use of the sole.

[0025] Furthermore, the zirconia foam ceramic particles are also provided with three-dimensional interpenetrating basalt chopped fibers. The basalt chopped fibers.

[0026] Through the above technical scheme, the present application significantly enhances the strength and toughness of the material by introducing three-dimensional interpenetrating basalt chopped fibers into zirconia foam ceramic particles. The basalt fibers have excellent tensile strength and can effectively disperse external impact forces and reduce the risk of material breakage. At the same time, after the fibers are entangled with the zirconia foam ceramic particles and added, the bonding strength between the porous inorganic modified particles and the EVA resin matrix can be significantly improved, thereby further improving the wear resistance and durability of the EVA thermoplastic elastomer shoe material.

[0027] Furthermore, the surface of the porous inorganic modified particles is coated with a compatible modified layer.

[0028] Furthermore, the compatible modified layer is a polyvinyl acetate coating layer.

[0029] Furthermore, the porous inorganic modified particles coated with the compatible modified layer are prepared by the following scheme:

[0030] The porous inorganic modified particles are immersed in a sodium dodecylbenzene sulfonate solution and allowed to stand for 24 hours, filtered and dried, and the surface pretreated porous inorganic modified particles are collected;

[0031] The surface pretreated porous inorganic modified particles, vinyl acetate monomer and ammonium persulfate are stirred and mixed and placed in a nitrogen atmosphere. After the reaction is stirred and heated, the mixture is allowed to stand after demulsification, the lower turbid liquid is collected and centrifuged, and the precipitate is collected and dried to prepare the porous inorganic modified particles coated with the compatible modified layer.

[0032] Through the above technical scheme, the present application coats the surface of the porous inorganic modified particles with a polyvinyl acetate coating layer. Since polyvinyl acetate can not only improve the dispersion performance of the porous inorganic modified particles in the polyvinyl acetate coating layer, but the polyvinyl acetate coating layer can also effectively improve the compatibility between the thermoplastic polyamide elastomer and the EVA resin, the technical scheme of the present application further improves the mechanical properties and structural strength of the EVA thermoplastic elastomer shoe material by preparing the porous inorganic modified particles coated with the compatible modified layer.

[0033] In a second aspect, the present application provides a method for preparing a thermoplastic elastomer shoe material, using the following technical solution:

[0034] A method for preparing a thermoplastic elastomer shoe material comprises the following preparation steps:

[0035] Taking modified resin particles and porous inorganic modified particles coated with a compatible modified layer, stirring and mixing them, placing them in an extruder, melting and extruding, and collecting the mixed particles;

[0036] The mixed particles are mixed with EVA resin, and a foaming agent, an antioxidant, a compatibilizer and zinc stearate are added and stirred and mixed. The mixture is kneaded and placed in a vulcanization device. The thermoplastic elastomer shoe material can be prepared by vulcanization.

[0037] Through the above technical scheme, the present application first mixes the modified resin particles with the porous inorganic modified particles coated with the compatible modification layer, thereby improving the dispersion performance of the porous inorganic modified particles and improving the compatibility between the modified resin particles and the EVA resin particles, thereby ensuring sufficient mixing and uniform distribution of the components. This method not only improves production efficiency, but also effectively controls the quality and performance of the products, ensuring the performance and stability of the shoe materials.

[0038] Furthermore, the compatibilizer is EVA-g-MAH polymer.

[0039] In summary, this application has the following beneficial effects:

[0040] First, this application combines the excellent mechanical properties of thermoplastic polyamide elastomers with the flexibility of EVA. Since the molecular structure of thermoplastic polyamide elastomers has high strength and toughness, it can effectively disperse and absorb the external pressure and impact force applied to the material, reducing the wear caused by friction. In addition, the heat resistance and chemical resistance of thermoplastic polyamide elastomers make the material stable under high temperature and harsh environments, not easy to age and deform, thereby extending the service life. This application optimizes the composition ratio of thermoplastic polyamide elastomer and EVA to form a uniform interlaced network structure, enhances the tear resistance and impact resistance of the shoe material, and makes the modified EVA material show excellent wear resistance and mechanical properties in practical applications.

[0041] Second, the application selects zirconia foam ceramic particles as porous inorganic modified particles, which have significant wear resistance and impact resistance. The lightweight characteristics of zirconia foam ceramic particles combined with durability allow the sole to remain light while also being able to withstand greater pressure and impact.

[0042] Based on the above scheme, the present application makes the final product have good mechanical properties and thermal stability through the mixed reaction of zirconium oxychloride and ethanol, combined with the subsequent aging and calcination steps. This technical solution makes the manufacturing process highly controllable, and the particles finally obtained can effectively improve the comprehensive performance of the shoe material, especially in terms of wear resistance and impact resistance, ensuring the long-term use of the sole.

[0043] Third, the present application coats the surface of the porous inorganic modified particles with a polyvinyl acetate coating layer. Since polyvinyl acetate can not only improve the dispersion performance of the porous inorganic modified particles in the polyvinyl acetate coating layer, but the polyvinyl acetate coating layer can also effectively improve the compatibility between the thermoplastic polyamide elastomer and the EVA resin, the technical solution of the present application further improves the mechanical properties and structural strength of the EVA thermoplastic elastomer shoe material by preparing the porous inorganic modified particles coated with the compatible modified layer. DETAILED DESCRIPTION

[0044] The present application is further described in detail below with reference to the embodiments.

[0045] In the examples of the present application, the raw materials and instruments used are as follows, but not limited thereto. Raw materials not otherwise specified are of analytical grade.

[0046] Polyether block amide: Arkema, France, brand 2533SA01;

[0047] EVA: Japan Mitsui, brand 210.

[0048] Preparation Example

[0049] Preparation Example 1

[0050] 50 g of zirconium oxychloride was placed in 800 g of 35% ethanol and stirred until the zirconium oxychloride was dissolved, 10 g of yttrium nitrate and 50 g of 15% nitric acid were added and mixed, and after flocculent precipitation appeared, 30 g of formamide and 15 g of polyethylene glycol were added and stirred, and the mixed solution was collected;

[0051] 500 g of the mixed solution was mixed with 2.0 kg of propylene oxide and allowed to stand for aging for 24 h, the sol solution was collected and washed with anhydrous ethanol, and dried in an oven at 60 ° C for 24 h to obtain an aerogel;

[0052] Take 20g of aerogel and 50g of zirconium oxychloride, stir and mix, add 1200g of deionized water, stir and collect to obtain slurry, take 200g of slurry and 1000g of 10% by mass polyethylene glycol / hydrogen peroxide solution, stir and mix, put it in a mold, dry and transfer it to a calcining furnace, after sintering, let it stand and cool to room temperature, crush, grind and sieve, and then zirconium oxide foam ceramic particles 1 can be prepared.

[0053] Preparation Example 2

[0054] 65 g of zirconium oxychloride was placed in 1000 g of 35% ethanol and stirred until the zirconium oxychloride was dissolved, 10 g of yttrium nitrate and 50 g of 15% nitric acid were added and mixed, and after flocculent precipitation appeared, 32 g of formamide and 17 g of polyethylene glycol were added and stirred, and the mixed solution was collected;

[0055] 650 g of the mixed solution was mixed with 2.2 kg of propylene oxide and allowed to stand for aging for 24 h, the sol solution was collected and washed with anhydrous ethanol, and dried in an oven at 60 ° C for 24 h to obtain an aerogel;

[0056] Take 22g of aerogel and 50g of zirconium oxychloride, stir and mix, add 1350g of deionized water, stir and collect to obtain slurry, take 200g of slurry and 1000g of 10% by mass polyethylene glycol / hydrogen peroxide solution, stir and mix, put it in a mold, dry and transfer it to a calcining furnace, after sintering, let it stand and cool to room temperature, crush, grind and sieve, and then zirconium oxide foam ceramic particles 2 can be prepared.

[0057] Preparation Example 3

[0058] 80g of zirconium oxychloride was placed in 1200g of 35% ethanol and stirred until the zirconium oxychloride was dissolved, 10g of yttrium nitrate and 50g of 15% nitric acid were added and mixed, and after flocculent precipitation appeared, 35g of formamide and 20g of polyethylene glycol were added and stirred, and the mixed solution was collected;

[0059] 800 g of the mixed solution was mixed with 2.5 kg of propylene oxide and allowed to stand for aging for 24 h, the sol solution was collected and washed with anhydrous ethanol, and dried in an oven at 60 ° C for 24 h to obtain an aerogel;

[0060] Take 25g of aerogel and 50g of zirconium oxychloride, stir and mix, add 1500g of deionized water, stir and collect to obtain slurry, take 200g of slurry and 1000g of 10% by mass polyethylene glycol / hydrogen peroxide solution, stir and mix, put in a mold, dry and transfer to a calcining furnace, after sintering, let it stand and cool to room temperature, crush, grind and sieve, and then zirconium oxide foam ceramic particles 3 can be prepared.

[0061] Preparation Example 4

[0062] 80g of zirconium oxychloride was placed in 1200g of 35% ethanol and stirred until the zirconium oxychloride was dissolved, 10g of yttrium nitrate and 50g of 15% nitric acid were added and mixed, and after flocculent precipitation appeared, 35g of formamide and 20g of polyethylene glycol were added and stirred, and the mixed solution was collected;

[0063] 800 g of the mixed solution was mixed with 2.5 kg of propylene oxide and allowed to stand for aging for 24 h, the sol solution was collected and washed with anhydrous ethanol, and dried in an oven at 60 ° C for 24 h to obtain an aerogel;

[0064] Take 25g of aerogel and 50g of zirconium oxychloride, stir and mix, add 1500g of deionized water, stir and collect to obtain slurry, take 200g of slurry, 30g of basalt fiber and 1000g of 10% by mass polyethylene glycol / hydrogen peroxide solution, stir and mix, put in a mold, dry and transfer to a calcining furnace, after sintering, let it stand and cool to room temperature, crush, grind and sieve, and then zirconium oxide foam ceramic particles 4 can be prepared.

[0065] Preparation Example 5

[0066] Take the zirconium oxide foam ceramic particles 1 and immerse them in a 10% by mass sodium dodecylbenzene sulfonate solution and let it stand for 24 hours, filter and dry, and collect the surface pretreated porous inorganic modified particles;

[0067] Take 20g of surface pretreated porous inorganic modified particles, 40g of vinyl acetate monomer and 10g of 2.5% ammonium persulfate solution, stir and mix, and place in a nitrogen atmosphere. After stirring and reacting at 80°C for 5h, add 5% magnesium sulfate solution to break the emulsion and let it stand. Collect the lower turbid liquid and centrifuge it. Collect the precipitate and dry it to prepare the porous inorganic modified particles 1 coated with the compatible modification layer.

[0068] Preparation Example 6

[0069] Take the zirconium oxide foam ceramic particles 2 and immerse them in a 10% by mass sodium dodecylbenzene sulfonate solution and let it stand for 24 hours, filter and dry, and collect the surface pretreated porous inorganic modified particles;

[0070] Take 20g of surface pretreated porous inorganic modified particles, 40g of vinyl acetate monomer and 10g of 2.5% ammonium persulfate solution, stir and mix, and place in a nitrogen atmosphere. After stirring and reacting at 80°C for 5h, add 5% magnesium sulfate solution to break the emulsion and let it stand. Collect the lower turbid liquid and centrifuge it. Collect the precipitate and dry it to prepare the porous inorganic modified particles 2 coated with the compatible modification layer.

[0071] Preparation Example 7

[0072] Take the zirconium oxide foam ceramic particles 3 and immerse them in a 10% by mass sodium dodecylbenzene sulfonate solution and let it stand for 24 hours, filter and dry, and collect the surface pretreated porous inorganic modified particles;

[0073] Take 20g of surface pretreated porous inorganic modified particles, 40g of vinyl acetate monomer and 10g of 2.5% ammonium persulfate solution, stir and mix, and place in a nitrogen atmosphere. After stirring and reacting at 80°C for 5h, add 5% magnesium sulfate solution to break the emulsion and let it stand. Collect the lower turbid liquid and centrifuge it. Collect the precipitate and dry it to prepare the porous inorganic modified particles 3 coated with the compatible modification layer.

[0074] Preparation Example 8

[0075] Take the zirconium oxide foam ceramic particles 4 and immerse them in a 10% by mass sodium dodecylbenzene sulfonate solution and let it stand for 24 hours, filter and dry, and collect the surface pretreated porous inorganic modified particles;

[0076] Take 20g of surface pretreated porous inorganic modified particles, 40g of vinyl acetate monomer and 10g of 2.5% ammonium persulfate solution, stir and mix them, and place them in a nitrogen atmosphere. After stirring and reacting at 80°C for 5h, add 5% magnesium sulfate solution to break the emulsion and let it stand. Collect the lower turbid liquid and centrifuge it. Collect the precipitate and dry it to prepare the porous inorganic modified particles 4 coated with the compatible modification layer. Example 1

[0077] A thermoplastic elastomer shoe material is prepared from the following substances:

[0078] 20kg EVA resin, 3kg blowing agent azodicarbonamide, 0.1kg antioxidant 1010, 1kg EVA-g-MAH polymer, 1kg zinc stearate and 3kg polyether block amide.

[0079] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0080] The thermoplastic elastomer shoe material is prepared by mixing polyether block amide with EVA resin, adding a foaming agent, an antioxidant, a compatibilizer and zinc stearate, and mixing at 140° C. for 10 minutes, and then molding it in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. for 2 minutes. Example 2

[0081] A thermoplastic elastomer shoe material is prepared from the following substances:

[0082] 25kg EVA resin, 5kg foaming agent azodicarbonamide, 0.5kg antioxidant 1010, 3.5kg EVA-g-MAH polymer, 4kg zinc stearate and 5kg polyether block amide.

[0083] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0084] The thermoplastic elastomer shoe material is prepared by mixing polyether block amide with EVA resin, adding a foaming agent, an antioxidant, a compatibilizer and zinc stearate, and mixing at 140° C. for 10 minutes, and then molding it in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. for 2 minutes. Example 3

[0085] A thermoplastic elastomer shoe material is prepared from the following substances:

[0086] 30kg EVA resin, 8kg foaming agent azodicarbonamide, 1.0kg antioxidant 1010, 5kg EVA-g-MAH polymer, 5kg zinc stearate and 8kg polyether block amide.

[0087] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0088] The thermoplastic elastomer shoe material is prepared by mixing polyether block amide with EVA resin, adding a foaming agent, an antioxidant, a compatibilizer and zinc stearate, and mixing at 140° C. for 10 minutes, and then molding it in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. for 2 minutes.

[0089] Example 4

[0090] A thermoplastic elastomer shoe material is prepared from the following substances:

[0091] 25kg EVA resin, 5kg blowing agent azodicarbonamide, 0.5kg antioxidant 1010, 3.5kg EVA-g-MAH polymer, 4kg zinc stearate, 0.5kg porous inorganic modified particles 1 and 5kg polyether block amide.

[0092] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0093] The polyether block amide and the porous inorganic modified particles 1 are mixed and placed in an extruder, the die temperature of the extruder is controlled to be 145° C., the rotor speed is 55 r / min, and the mixed particles are melt-extruded and collected;

[0094] The mixed particles are mixed with EVA resin and a foaming agent, an antioxidant, a compatibilizer and zinc stearate are added and stirred. After kneading at 140° C. for 10 minutes, it is placed in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. and molded for 2 minutes to prepare the thermoplastic elastomer shoe material.

[0095] Example 5

[0096] A thermoplastic elastomer shoe material is prepared from the following substances:

[0097] 25kg EVA resin, 5kg blowing agent azodicarbonamide, 0.5kg antioxidant 1010, 3.5kg EVA-g-MAH polymer, 4kg zinc stearate, 1.5kg porous inorganic modified particles 2 and 5kg polyether block amide.

[0098] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0099] The polyether block amide and the porous inorganic modified particles 2 are mixed and placed in an extruder, the die temperature of the extruder is controlled at 145° C., the rotor speed is controlled at 55 r / min, and the mixed particles are melt-extruded and collected;

[0100] The mixed particles are mixed with EVA resin and a foaming agent, an antioxidant, a compatibilizer and zinc stearate are added and stirred. After kneading at 140° C. for 10 minutes, it is placed in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. and molded for 2 minutes to prepare the thermoplastic elastomer shoe material.

[0101] Example 6

[0102] A thermoplastic elastomer shoe material is prepared from the following substances:

[0103] 25kg EVA resin, 5kg blowing agent azodicarbonamide, 0.5kg antioxidant 1010, 3.5kg EVA-g-MAH polymer, 4kg zinc stearate, 3.0kg porous inorganic modified particles 3 and 5kg polyether block amide.

[0104] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0105] The polyether block amide and the porous inorganic modified particles 3 are mixed and placed in an extruder, and the die temperature of the extruder is controlled to be 145° C. and the rotor speed is 55 r / min. The mixed particles are melt-extruded and collected;

[0106] The mixed particles are mixed with EVA resin and a foaming agent, an antioxidant, a compatibilizer and zinc stearate are added and stirred. After kneading at 140° C. for 10 minutes, it is placed in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. and molded for 2 minutes to prepare the thermoplastic elastomer shoe material.

[0107] Example 7

[0108] A thermoplastic elastomer shoe material is prepared from the following substances:

[0109] 25kg EVA resin, 5kg foaming agent azodicarbonamide, 0.5kg antioxidant 1010, 3.5kg EVA-g-MAH polymer, 4kg zinc stearate, 1.5kg porous inorganic modified particles 4 and 5kg polyether block amide.

[0110] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0111] Take the polyether block amide and the porous inorganic modified particles 4, stir and mix them and place them in an extruder, control the extruder die temperature to 145° C., the rotor speed to 55 r / min, melt extrude and collect the mixed particles;

[0112] The mixed particles are mixed with EVA resin and a foaming agent, an antioxidant, a compatibilizer and zinc stearate are added and stirred. After kneading at 140° C. for 10 minutes, it is placed in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. and molded for 2 minutes to prepare the thermoplastic elastomer shoe material.

[0113] Example 8

[0114] A thermoplastic elastomer shoe material is prepared from the following substances:

[0115] 25kg EVA resin, 5kg azodicarbonamide as a foaming agent, 0.5kg antioxidant 1010, 3.5kg EVA-g-MAH polymer, 4kg zinc stearate, 1.5kg porous inorganic modified particles 1 coated with a compatible modified layer, and 5kg polyether block amide.

[0116] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0117] The polyether block amide and the porous inorganic modified particles 1 coated with a compatible modified layer are mixed and placed in an extruder, the die temperature of the extruder is controlled to be 145° C., the rotor speed is 55 r / min, and the mixed particles are melt-extruded and collected;

[0118] The mixed particles are mixed with EVA resin and a foaming agent, an antioxidant, a compatibilizer and zinc stearate are added and stirred. After kneading at 140° C. for 10 minutes, it is placed in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. and molded for 2 minutes to prepare the thermoplastic elastomer shoe material.

[0119] Example 9

[0120] A thermoplastic elastomer shoe material is prepared from the following substances:

[0121] 25kg EVA resin, 5kg azodicarbonamide as a foaming agent, 0.5kg antioxidant 1010, 3.5kg EVA-g-MAH polymer, 4kg zinc stearate, 1.5kg porous inorganic modified particles 2 coated with a compatible modified layer, and 5kg polyether block amide.

[0122] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0123] The polyether block amide and the porous inorganic modified particles 2 coated with a compatible modified layer are mixed and placed in an extruder, the die temperature of the extruder is controlled to be 145° C., the rotor speed is 55 r / min, and the mixed particles are melt-extruded and collected;

[0124] The mixed particles are mixed with EVA resin and a foaming agent, an antioxidant, a compatibilizer and zinc stearate are added and stirred. After kneading at 140° C. for 10 minutes, it is placed in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. and molded for 2 minutes to prepare the thermoplastic elastomer shoe material.

[0125] Example 10

[0126] A thermoplastic elastomer shoe material is prepared from the following substances:

[0127] 25kg EVA resin, 5kg azodicarbonamide as a foaming agent, 0.5kg antioxidant 1010, 3.5kg EVA-g-MAH polymer, 4kg zinc stearate, 1.5kg porous inorganic modified particles 3 coated with a compatible modified layer, and 5kg polyether block amide.

[0128] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0129] The polyether block amide and the porous inorganic modified particles 3 coated with a compatible modified layer are mixed and placed in an extruder, the die temperature of the extruder is controlled to be 145° C., the rotor speed is 55 r / min, and the mixed particles are melt-extruded and collected;

[0130] The mixed particles are mixed with EVA resin and a foaming agent, an antioxidant, a compatibilizer and zinc stearate are added and stirred. After kneading at 140° C. for 10 minutes, it is placed in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. and molded for 2 minutes to prepare the thermoplastic elastomer shoe material.

[0131] Embodiment 11

[0132] A thermoplastic elastomer shoe material is prepared from the following substances:

[0133] 25kg EVA resin, 5kg azodicarbonamide as a foaming agent, 0.5kg antioxidant 1010, 3.5kg EVA-g-MAH polymer, 4kg zinc stearate, 1.5kg porous inorganic modified particles 4 coated with a compatible modified layer, and 5kg polyether block amide.

[0134] A thermoplastic elastomer shoe material comprises the following preparation steps:

[0135] The polyether block amide and the porous inorganic modified particles 4 coated with a compatible modified layer are mixed and placed in an extruder, the die temperature of the extruder is controlled to be 145° C., the rotor speed is 55 r / min, and the mixed particles are melt-extruded and collected;

[0136] The mixed particles are mixed with EVA resin and a foaming agent, an antioxidant, a compatibilizer and zinc stearate are added and stirred. After kneading at 140° C. for 10 minutes, it is placed in a flat vulcanizer at a pressure of 10 MPa and a temperature of 120° C. and molded for 2 minutes to prepare the thermoplastic elastomer shoe material.

[0137] Comparative Example

[0138] Compared with Example 1, modified resin particles and compatibilizer were not added in this comparative example, and the remaining preparation steps and preparation methods were the same as those in Example 1.

[0139] Performance Testing

[0140] The thermoplastic elastomer shoe materials prepared in Examples 1-11 were subjected to performance tests:

[0141] The wear resistance is tested using a rubber wear testing machine in accordance with GB / T 9867-2008 “Determination of wear resistance of vulcanized rubber or thermoplastic rubber”.

[0142] The results are shown in Table 1 below:

[0143] Table 1 Performance test table

[0144]

[0145] From the above examples 1-11 and comparative example 1, combined with the test results in Table 1, it can be found that:

[0146] Combined with the test results of Examples 1-3 and Comparative Example 1, it is shown that the technical solution of the present application combines the excellent mechanical properties of thermoplastic polyamide elastomer with the flexibility of EVA to effectively disperse and absorb the external pressure and impact force applied to the material, reduce the wear caused by friction, and enhance the wear resistance and mechanical properties of the shoe material.

[0147] By comparing Examples 4-6 with Examples 1-3, it is shown that the technical solution of the present application has significant wear resistance and impact resistance by selecting zirconium oxide foam ceramic particles as porous inorganic modified particles.

[0148] By comparing Example 7 with Examples 4-6, it is shown that the technical solution of the present application significantly enhances the strength and toughness of the material by introducing three-dimensional interpenetrating basalt chopped fibers into the zirconia foam ceramic particles. The basalt fibers have excellent tensile strength, can effectively disperse external impact forces, and reduce the risk of material breakage. At the same time, after the fibers are entangled with the zirconia foam ceramic particles and added, the bonding strength between the porous inorganic modified particles and the EVA resin matrix can be significantly improved, thereby further improving the wear resistance and durability of the EVA thermoplastic elastomer shoe material.

[0149] Finally, by comparing Examples 8-11 and Examples 4-7 of the technical scheme of the present application, it is explained that the technical scheme of the present application, by coating the surface of the porous inorganic modified particles with a polyvinyl acetate coating layer, polyvinyl acetate can not only improve the dispersion performance of the porous inorganic modified particles in the polyvinyl acetate coating layer, but the polyvinyl acetate coating layer can also effectively improve the compatibility between the thermoplastic polyamide elastomer and the EVA resin. Therefore, the technical scheme of the present application further improves the mechanical properties and structural strength of the EVA thermoplastic elastomer shoe material by preparing porous inorganic modified particles coated with a compatible modified layer.

[0150] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached claims.

[0151] All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of a conflict, the definition in this specification shall prevail.

[0152] When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.

[0153] In the context of the present specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.

Claims

1. A thermoplastic elastomer shoe material, characterized in that: The composition includes the following materials in parts by weight: 20-30 parts of EVA resin; 3-8 parts of foaming agent; Antioxidant 0.1-1.0 part; 1-5 parts of compatibilizer; 1-5 parts of zinc stearate; 3-8 parts of modified resin particles; The modified resin particles are thermoplastic polyamide elastomers, and the polyamide elastomers include at least one of polyether block amide and polyester amide; The thermoplastic elastomer shoe material further comprises 0.5-3.0 parts of porous inorganic modified particles; The porous inorganic modified particles are foamed ceramic particles, and the foamed ceramic particles are zirconium oxide foamed ceramic particles.

2. A thermoplastic elastomer shoe material according to claim 1, characterized in that: The zirconia foam ceramic particles are made by the following technical solution: Zirconium oxychloride is placed in ethanol and stirred, yttrium nitrate and nitric acid are added and mixed, after flocculent precipitation occurs, formamide and polyethylene glycol are added and stirred, and a mixed solution is collected; The mixed solution is mixed with propylene oxide and stirred and allowed to stand for aging, and the sol solution is collected and washed and dried to obtain an aerogel; The aerogel is mixed with zirconium oxychloride and deionized water is added, and the slurry is collected by stirring. The slurry is mixed with a polyethylene glycol / hydrogen peroxide solution and placed in a mold. The mixture is dried and transferred to a calcining furnace. After sintering, the mixture is allowed to stand and cool to room temperature, and then the mixture is crushed, ground and sieved to prepare zirconium oxide foam ceramic particles.

3. A thermoplastic elastomer shoe material according to claim 1, characterized in that: The zirconium oxide foam ceramic particles are also provided with three-dimensional interpenetrating basalt chopped fibers.

4. The thermoplastic elastomer shoe material according to claim 1, characterized in that: The surface of the porous inorganic modified particles is coated with a compatible modified layer.

5. A thermoplastic elastomer shoe material according to claim 4, characterized in that: The compatible modified layer is a polyvinyl acetate coating layer.

6. A thermoplastic elastomer shoe material according to claim 4, characterized in that: The porous inorganic modified particles coated with the compatible modified layer are prepared by the following scheme: The porous inorganic modified particles are immersed in a sodium dodecylbenzene sulfonate solution and allowed to stand for 24 hours, filtered and dried, and the surface pretreated porous inorganic modified particles are collected; The surface pretreated porous inorganic modified particles, vinyl acetate monomer and ammonium persulfate are stirred and mixed and placed in a nitrogen atmosphere. After the reaction is stirred and heated, the mixture is allowed to stand after demulsification, the lower turbid liquid is collected and centrifuged, and the precipitate is collected and dried to prepare the porous inorganic modified particles coated with the compatible modified layer.

7. A method for preparing a thermoplastic elastomer shoe material, used for producing the thermoplastic elastomer shoe material according to any one of claims 1 to 6, characterized in that: The method comprises the following preparation steps: Taking modified resin particles and porous inorganic modified particles coated with a compatible modified layer, stirring and mixing them, placing them in an extruder, melting and extruding, and collecting the mixed particles; The mixed particles are mixed with EVA resin, and a foaming agent, an antioxidant, a compatibilizer and zinc stearate are added and stirred and mixed. The mixture is kneaded and placed in a vulcanization device. The thermoplastic elastomer shoe material can be prepared by vulcanization.

8. The method for preparing a thermoplastic elastomer shoe material according to claim 7, characterized in that: The compatibilizer is EVA-g-MAH polymer.

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