High-resilience antibacterial breathable insole foaming material and preparation method thereof

Abstract

According to the high-resilience antibacterial breathable insole foaming material and the preparation method thereof, self-made polymer high-elasticity microspheres serve as a high-resilience material, self-made three-dimensional flower-shaped zinc oxide is loaded with water-drop-shaped copper oxide to serve as a breathable antibacterial material, the special three-dimensional structure of the three-dimensional flower-shaped zinc oxide is utilized, and the high-resilience antibacterial breathable insole foaming material is prepared. The high-resilience antibacterial breathable insole foaming material can effectively provide large specific surface area and space, meanwhile, water-drop-shaped copper oxide is loaded on the surface of the high-resilience antibacterial breathable insole foaming material, the special water-drop-shaped structure of the high-resilience antibacterial breathable insole foaming material can effectively pierce the surface of bacteria so as to achieve a remarkable antibacterial effect, and the high-resilience antibacterial breathable insole foaming material is prepared by combining a supercritical foaming process. The high resilience and long-acting breathable and antibacterial effects of the foaming material are realized.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of foamed materials, especially to a kind of high resilience antibacterial breathable midsole foamed material. BACKGROUND

[0002] High resilience foamed material has the advantages of high elasticity, low hysteresis loss, high compression load ratio, etc., and is widely used in fields such as household, transportation, medical, sports, toys, industrial protection, etc., which are often in contact with human body. However, due to the porosity and hygroscopicity of foamed materials, their products are easy to stain sweat and various stains, causing the growth of bacteria and harm to the environment and human health. Therefore, the development of high resilience antibacterial breathable foamed material is of great significance to protect human health and has broad prospects. SUMMARY

[0003] To solve the technical problems of high resilience antibacterial breathable foamed material mentioned in the background art, the purpose of the present application is to develop a kind of high resilience antibacterial breathable midsole foamed material, which realizes high resilience of foamed material and solves the problems of antibacterial and breathability, and improves the application field of products. In order to achieve the above purpose, the technical scheme adopted by the present application is as follows: A kind of high resilience antibacterial breathable midsole foamed material and its preparation method, including the following components by weight fraction: base resin 50~80 parts; high resilience material 5~15 parts; breathable antibacterial material 5~10 parts; lubricant 0.5~1.5 parts; crosslinking agent 0.5~2 parts; blending agent 1~5 parts.

[0004] As a preferred scheme, the base resin is at least two of EVA, POE, TPEE and TPE.

[0005] As a preferred scheme, the high resilience material is a polymer high elasticity microsphere, and its preparation method includes the following steps: Step one: weigh 150~300g of polyvinyl alcohol aqueous solution, add 2~5g of sodium pyrophosphate, and magnetically stir for 30~60min until dissolved uniformly, then place in a constant temperature cold bath pot to obtain solution A, ready for use; Step two: respectively weigh 2~5g of aminopropylmethylsiloxane-dimethylsiloxane copolymer dissolved in 5~20mL of dichloromethane; 1~3g of dialdehyde-terminated polydimethylsiloxane is dissolved in 2~10mL of tetrahydrofuran, and the above two polysiloxane solutions are mixed uniformly to obtain solution B; Step three: slowly add solution B into solution A, emulsify for 10-30 min at a stirring rate of 300-500 / min, then increase the temperature to 50-80℃ and react for 3-6 h, after that, centrifuge the emulsion at high speed, wash the upper layer of microspheres with deionized water, clean with ethanol and centrifuge for 3-6 times, and finally dry for 12-24 h to obtain the polymer high-elasticity microspheres, which are tested to have an average particle size ranging from 150 nm to 400 nm.

[0006] As a preferred solution, the air-permeable bacteriostatic material is three-dimensional flower-shaped zinc oxide loaded water-drop-shaped copper oxide, and a preparation method thereof comprises the following steps: Step one: weigh 0.1-0.5 g of zinc acetate dihydrate, dissolve it in a 0.5-1 mol / L sodium hydroxide aqueous solution, add zinc sheet, ultrasonic treat for 10-30 min, and then move it to a stainless steel reaction kettle to obtain a milky white mixed solution; Step two: place the milky white solution obtained in step one in an oven at 50-80℃, and fully hydrothermally react for 24-48 h until the reaction is complete, take out the zinc sheet, and repeatedly wash it with deionized water and ethanol for 3-5 times, and then dry it in an oven at 50-80℃ to obtain three-dimensional flower-shaped zinc oxide; Step three: weigh copper acetate and sodium tetraborate decahydrate (molar ratio 1:5-10), respectively dissolve them in deionized water, uniformly disperse them by ultrasonic treatment to obtain a copper acetate-sodium borate mixed solution, slowly add an amphoteric surfactant under magnetic stirring, fully react for 30-60 min, and then add the three-dimensional flower-shaped zinc oxide obtained in step two to obtain a blue mixed solution; Step four: move the blue mixed solution obtained in step three into a reaction kettle, react in an electric heating constant temperature air drying oven, naturally cool to room temperature after the reaction, centrifuge the product, wash it with deionized water and anhydrous ethanol alternately for three times, precipitate it in a vacuum drying oven at 60℃ for 5 h, and finally obtain three-dimensional flower-shaped zinc oxide loaded water-drop-shaped copper oxide.

[0007] As a preferred solution, the amphoteric surfactant in step three is at least one of cocamidopropylamine oxide, lauramidopropylamine oxide, and dodecyl ethoxy sulfobetaine, and the molar ratio of the surfactant to copper acetate is 1:(50-100).

[0008] As a preferred solution, the reaction temperature in the reaction kettle in step four is 150℃-220℃, and the reaction time is 10-20 h.

[0009] As a preferred solution, the lubricant is at least one of stearic acid, zinc stearate, and EVA wax.

[0010] As a preferred solution, the crosslinking agent is dicumyl peroxide.

[0011] As a preferred solution, the blending agent is diethyl 2-oxopropandioate and ethyleneglycol diethylether diamine tetraacetic acid with a mass ratio of 2:3~5.

[0012] As a preferred solution, the preparation method of the high-resilience antibacterial and breathable midsole foaming material comprises the following steps: Step one: the base resin, high-resilience material, breathable and antibacterial material, lubricant, crosslinking agent, blending agent are sequentially added into a high-speed mixer in weight percentage, and high-speed mixing is conducted to obtain a premix; Step two: the premix obtained in step one is added into a double-screw extruder, and processes such as supercritical CO2 injection, shearing and mixing, pressure reduction and extrusion, temperature increase and foaming, and cooling and shaping are conducted to obtain the high-resilience antibacterial and breathable midsole foaming material.

[0013] Compared with the prior art, the present application has the following beneficial effects: (1) The self-made polymer high-elasticity microspheres are used as the high-resilience material, the special microsphere structure of the polymer high-elasticity microspheres is utilized, and the supercritical foaming forming technology is combined to effectively improve the resilience performance of the foaming material.

[0014] (2) The self-made three-dimensional flower-shaped zinc oxide loaded with water-drop-shaped copper oxide is used as the breathable and antibacterial material, the special three-dimensional structure of the three-dimensional flower-shaped zinc oxide is utilized to effectively provide a large specific surface area and space, and the water-drop-shaped copper oxide is loaded on the surface of the three-dimensional flower-shaped zinc oxide, the special water-drop-shaped structure of the water-drop-shaped copper oxide can effectively pierce the surface of bacteria to achieve a significant antibacterial effect, and the long-acting breathable and antibacterial effect of the foaming material is realized. DETAILED DESCRIPTION

[0015] The present application will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present application, but do not limit the present application in any form. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present application. These all belong to the protection scope of the present application. Example 1

[0016] A high-resilience antibacterial and breathable midsole foaming material and a preparation method thereof comprise the following components in weight percentage: EVA resin 30 parts; TPEE resin 30 parts; high-resilience material 10 parts; breathable and antibacterial material 10 parts; zinc stearate 1 part; dicumyl peroxide 1 part; diethyl 2-oxopropandioate and ethyleneglycol diethylether diamine tetraacetic acid (mass ratio 2:3) 2 parts.

[0017] The high-resilience material is polymer high-elasticity microspheres, and the preparation method thereof comprises the following steps: Step one: take 150~300g of polyvinyl alcohol aqueous solution, add 2~5g of sodium pyrophosphate, magnetically stir for 30~60min until dissolved uniformly and then place in a constant temperature cold bath pot to obtain solution A, ready for use; Step two: respectively take 2~5g of aminopropylmethylsiloxane-dimethylsiloxane copolymer dissolved in 5~20mL of dichloromethane; 1~3g of dialdehyde terminated polydimethylsiloxane dissolved in 2~10mL of tetrahydrofuran, mix the above two polysiloxane solutions uniformly to obtain solution B; Step three: slowly add solution B to solution A, emulsify at a stirring rate of 300~500 / min for 10~30min, then heat to 50~80℃ and react for 3~6h, then centrifuge the emulsion, wash the upper microspheres with deionized water, ethanol and centrifuge for 3~6 times, and finally dry for 12~24h to obtain polymer high elasticity microspheres, which are tested to have an average particle size range of 150~400nm.

[0018] The air-permeable bacteriostatic material is three-dimensional flower-shaped zinc oxide loaded with water droplet-shaped copper oxide, and its preparation method comprises the following steps: Step one: take 0.1~0.5g of zinc acetate dihydrate and dissolve it in a 0.5~1mol / L sodium hydroxide aqueous solution, add zinc sheet, ultrasonic treatment for 10~30min, then move to a stainless steel reaction kettle to obtain a milky white mixed solution; Step two: place the milky white solution obtained in step one in a 50~80℃ oven, fully hydrothermal reaction for 24~48h until the reaction is complete, remove the zinc sheet and wash it repeatedly with deionized water and ethanol for 3~5 times, and then dry it in an oven at 50~80℃ to obtain three-dimensional flower-shaped zinc oxide; Step three: take copper acetate and sodium tetraborate decahydrate (molar ratio 1:5~10) and dissolve them in deionized water, respectively, and ultrasonic dispersion to obtain a copper acetate-sodium borate mixed solution, slowly add cocamide propyl oxide (molar ratio of cocamide propyl oxide to copper acetate is 1:50) while magnetically stirring, fully react for 30~60min, then add the three-dimensional flower-shaped zinc oxide obtained in step two to obtain a blue mixed solution; Step four: move the blue mixed solution obtained in step three into a reaction kettle and react in an electric heating constant temperature air drying oven, the reaction temperature is 200℃ and the reaction time is 12h, after the reaction, naturally cool to room temperature, centrifuge the product, wash it with deionized water and anhydrous ethanol alternately for three times, precipitate and dry in a vacuum drying oven at 60℃ for 5h, and finally obtain three-dimensional flower-shaped zinc oxide loaded with water droplet-shaped copper oxide.

[0019] The preparation method of the high-resilience bacteriostatic air-permeable midsole foaming material comprises the following steps: Step one: the base resin, high resilience material, breathable antibacterial material, lubricant, crosslinking agent, blending agent, according to the weight fraction is added into the high-speed mixer in turn, high-speed mixing, get premix; Step two: the premix obtained in step one is added to the twin-screw extruder, through the injection of supercritical CO2, shear mixing, pressure reduction extrusion, temperature rising foaming, cooling and shaping process, get high resilience antibacterial breathable midsole foaming material. Example 2

[0020] A kind of high resilience antibacterial breathable midsole foaming material and its preparation method, including the following components by weight fraction: EVA resin 25 parts; POE resin 25 parts; High resilience material 12.5 parts; Breathable antibacterial material 7.5 parts; EVA wax 0.75 parts; 0.75 parts of dicumyl peroxide; 2-oxo malonic acid diethyl ester and ethylene glycol diethyl ether diamine tetraacetic acid (mass ratio is 2:4) 1.5 parts.

[0021] The high resilience material is polymeric high elasticity microspheres, and its preparation method comprises the following steps: Step one: weigh 150~300g of polyvinyl alcohol aqueous solution, add 2~5g of sodium pyrophosphate, magnetically stir for 30~60min until dissolved uniformly, then place in a constant temperature cold bath pot to obtain solution A, ready for use; Step two: respectively weigh 2~5g of aminopropyl methyl siloxane-dimethyl siloxane copolymer dissolved in 5~20mL of dichloromethane; 1~3g of dialdehyde-terminated polydimethylsiloxane is dissolved in 2~10mL of tetrahydrofuran, the two polysiloxane solutions are mixed uniformly to obtain solution B; Step three: slowly add solution B to solution A, emulsify at a stirring rate of 300~500 / min for 10~30min, then heat to 50~80℃ and react for 3~6h, then centrifuge the emulsion at high speed, wash the upper microspheres with deionized water, ethanol and centrifuge for 3~6 times, and finally dry for 12~24h to obtain polymeric high elasticity microspheres, which are tested to have an average particle size range of 150~400nm.

[0022] The breathable antibacterial material is three-dimensional flower-shaped zinc oxide loaded with water droplet-shaped copper oxide, and its preparation method comprises the following steps: Step one: weigh 0.1~0.5g of zinc acetate dihydrate and dissolve it in a 0.5~1mol / L sodium hydroxide aqueous solution, add zinc sheet, ultrasonic treatment for 10~30min, then move to a stainless steel reaction kettle to obtain a milky white mixed solution; Step two: the milky white solution prepared in step one is placed in an oven at 50-80℃, and is subjected to hydrothermal reaction for 24-48h until the reaction is complete. The zinc sheet is washed repeatedly with deionized water and ethanol for 3-5 times, and is dried in an oven at 50-80℃ to obtain three-dimensional flower-like zinc oxide; Step three: copper acetate and sodium tetraborate decahydrate (molar ratio 1:5-10) are weighed and dissolved in deionized water respectively, and are uniformly dispersed by ultrasonic to obtain a mixed solution of copper acetate-sodium borate. While being magnetically stirred, lauryl amido propyl amine oxide is slowly added (the molar ratio of lauryl amido propyl amine oxide to copper acetate is 1:65), and the three-dimensional flower-like zinc oxide prepared in step two is added after 30-60min of sufficient reaction to obtain a blue mixed solution; Step four: the blue mixed solution prepared in step three is moved into a reaction kettle, and is reacted in an electric heating constant temperature air drying oven. The reaction temperature is 150℃, and the reaction time is 20h. After the reaction, the product is naturally cooled to room temperature, is centrifuged, is washed with deionized water and anhydrous ethanol alternately for three times, is precipitated, and is dried in a vacuum drying oven at 60℃ for 5h. Finally, three-dimensional flower-like zinc oxide loaded with water droplet-like copper oxide is obtained.

[0023] The preparation method of the high-rebound antibacterial and breathable midsole foaming material comprises the following steps: Step one: base resin, high-rebound material, breathable and antibacterial material, lubricant, crosslinking agent, blending agent, are sequentially added into a high-speed mixer according to weight fractions, and are subjected to high-speed mixing to obtain a premix; Step two: the premix obtained in step one is added into a double-screw extruder, and is subjected to processes such as injection of supercritical CO2, shear mixing, pressure reduction extrusion, temperature increase foaming, and cooling shaping to obtain the high-rebound antibacterial and breathable midsole foaming material. Example 3

[0024] A high-rebound antibacterial and breathable midsole foaming material and a preparation method thereof comprise the following components according to weight fractions: POE resin 40 parts; TPE resin 20 parts; high-rebound material 15 parts; breathable and antibacterial material 10 parts; stearic acid 1.25 parts; dicumyl peroxide 1.25 parts; 2-oxopropandioic acid diethyl ester and ethylene glycol diethyl ether diamine tetraacetic acid (mass ratio 2:5) 2 parts.

[0025] The high-rebound material is a polymer high-elasticity microsphere, and the preparation method thereof comprises the following steps: Step one: 150-300g of polyvinyl alcohol aqueous solution is weighed, 2-5g of sodium pyrophosphate is added, and the mixture is subjected to magnetic stirring for 30-60min until it is uniformly dissolved and is then placed in a constant-temperature cold bath pot to obtain solution A for standby use; Step two: 2-5 g of amino propyl methyl siloxane-dimethyl siloxane copolymer was respectively dissolved in 5-20 mL of dichloromethane; 1-3 g of dialdehyde terminated polydimethylsiloxane was dissolved in 2-10 mL of tetrahydrofuran, and the above two polysiloxane solutions were mixed uniformly to obtain solution B; Step three: solution B was slowly added to solution A, and was fully emulsified at a stirring rate of 300-500 / min for 10-30 min, then was heated to 50-80℃ for fully reacting for 3-6 h, and then the emulsion was centrifuged at high speed, the upper microspheres were washed with deionized water, ethanol and centrifuged for 3-6 times, and finally was dried for 12-24 h to obtain the polymer high-elasticity microspheres, which were tested to have an average particle size range of 150-400 nm.

[0026] The air-permeable bacteriostatic material is three-dimensional flower-shaped zinc oxide loaded with water-drop-shaped copper oxide, and a preparation method thereof comprises the following steps: Step one: 0.1-0.5 g of zinc acetate dihydrate was dissolved in a 0.5-1 mol / L sodium hydroxide aqueous solution, zinc sheet was added, and ultrasonic treatment was performed for 10-30 min, and then the mixture was transferred to a stainless steel reaction kettle to obtain a milky white mixed solution; Step two: the milky white solution obtained in step one was placed in an oven at 50-80℃ for hydrothermal reaction for 24-48 h until the reaction was complete, the zinc sheet was removed and washed repeatedly with deionized water and ethanol for 3-5 times, and then was dried in an oven at 50-80℃ to obtain three-dimensional flower-shaped zinc oxide; Step three: copper acetate and sodium tetraborate decahydrate (molar ratio 1:5-10) were respectively dissolved in deionized water, and were uniformly dispersed by ultrasonic treatment to obtain a copper acetate-sodium borate mixed solution, and dodecyl ethoxy sulfobetaine was slowly added under magnetic stirring (the molar ratio of dodecyl ethoxy sulfobetaine to copper acetate was 1:55), and fully reacted for 30-60 min, and then the three-dimensional flower-shaped zinc oxide obtained in step two was added to obtain a blue mixed solution; Step four: the blue mixed solution obtained in step three was transferred to a reaction kettle and reacted in an electric heating constant temperature air drying oven, the reaction temperature was 175℃, and the reaction time was 18 h, and after the reaction, the product was naturally cooled to room temperature, centrifuged, washed with deionized water and anhydrous ethanol alternately for three times, precipitated in a vacuum drying oven at 60℃ for 5 h, and finally three-dimensional flower-shaped zinc oxide loaded with water-drop-shaped copper oxide was obtained.

[0027] The preparation method of the high-resilience bacteriostatic air-permeable midsole foaming material comprises the following steps: Step one: the base resin, high-resilience material, air-permeable bacteriostatic material, lubricant, crosslinking agent, blending agent were sequentially added into a high-speed mixer according to the weight fraction, and were high-speed mixed to obtain a premix; Step two: the premix obtained in step one is added into a twin-screw extruder, and the high-rebound antibacterial and breathable midsole foaming material is obtained through the processes of supercritical CO2 injection, shearing mixing, pressure reduction extrusion, temperature rising foaming, cooling and shaping, etc. Example 4

[0028] A high-rebound antibacterial and breathable midsole foaming material and a preparation method thereof, comprising the following components in parts by weight: TPEE resin 35 parts; TPE resin 30 parts; high-rebound material 13 parts; breathable antibacterial material 8.5 parts; zinc stearate 1.5 parts; dicumyl peroxide 1.5 parts; 2-oxalacetic acid diethyl ester and ethylene glycol diethyl ether diamine tetraacetic acid (mass ratio 2:3) 2.5 parts.

[0029] The high-rebound material is a polymer high-elasticity microsphere, and the preparation method thereof comprises the following steps: Step one: weigh 150-300g of polyvinyl alcohol aqueous solution, add 2-5g of sodium pyrophosphate, and magnetically stir for 30-60min until dissolved uniformly, then place in a constant-temperature cold bath pot to obtain solution A for standby; Step two: respectively weigh 2-5g of aminopropylmethylsiloxane-dimethylsiloxane copolymer and dissolve in 5-20mL of dichloromethane; 1-3g of dialdehyde-terminated polydimethylsiloxane is dissolved in 2-10mL of tetrahydrofuran, and the above two polysiloxane solutions are mixed uniformly to obtain solution B; Step three: slowly add solution B to solution A, emulsify at a stirring rate of 300-500 / min for 10-30min, then heat to 50-80℃ and react for 3-6h, then centrifuge the emulsion at high speed, and wash and centrifuge the upper microspheres with deionized water and ethanol 3-6 times, and finally dry for 12-24h to obtain polymer high-elasticity microspheres, which are tested to have an average particle size range of 150-400nm.

[0030] The breathable antibacterial material is three-dimensional flower-shaped zinc oxide loaded with water droplet-shaped copper oxide, and the preparation method thereof comprises the following steps: Step one: weigh 0.1-0.5g of zinc acetate dihydrate and dissolve in a 0.5-1mol / L sodium hydroxide aqueous solution, add zinc sheet, ultrasonic treat for 10-30min, then move to a stainless steel reaction kettle to obtain a milky white mixed solution; Step two: place the milky white solution obtained in step one in an oven at 50-80℃, and fully hydrothermally react for 24-48h until the reaction is complete, take out the zinc sheet and wash with deionized water and ethanol for 3-5 times, and dry in an oven at 50-80℃ to obtain three-dimensional flower-shaped zinc oxide. Step three: copper acetate and sodium tetraborate decahydrate (molar ratio 1:5~10) were weighed and dissolved in deionized water respectively, and then uniformly dispersed by ultrasonic to obtain a copper acetate-sodium borate mixed solution. While being magnetically stirred, cocamidopropylamine oxide was slowly added (the molar ratio of cocamidopropylamine oxide to copper acetate was 1:75), and then the three-dimensional flower-like zinc oxide prepared in step two was added after fully reacting for 30~60 min to obtain a blue mixed solution; Step four: the blue mixed solution prepared in step three was moved into a reaction kettle, and reacted in an electric heating constant temperature air drying oven. The reaction temperature was 160℃, and the reaction time was 19h. After the reaction, it was naturally cooled to room temperature to obtain a product. The product was centrifuged, washed with deionized water and anhydrous ethanol alternately for three times, precipitated and dried in a vacuum drying oven at 60℃ for 5h, and finally three-dimensional flower-like zinc oxide loaded water droplet-like copper oxide was obtained.

[0031] The preparation method of the high-rebound antibacterial and breathable midsole foaming material comprises the following steps: Step one: base resin, high-rebound material, breathable and antibacterial material, lubricant, crosslinking agent, blending agent were sequentially added into a high-speed mixer according to weight fractions, and high-speed mixing was performed to obtain a premix; Step two: the premix obtained in step one was added into a double screw extruder, and then supercritical CO2 injection, shear mixing, pressure reduction extrusion, temperature rising foaming, cooling and shaping were performed to obtain the high-rebound antibacterial and breathable midsole foaming material. Comparative example 1

[0032] An antibacterial and breathable midsole foaming material and a preparation method thereof comprise the following components according to weight fractions: EVA resin 30 parts; TPEE resin 30 parts; breathable and antibacterial material 10 parts; zinc stearate 1 part; dicumyl peroxide 1 part; 2-oxopropandioic acid diethyl ester and ethylene glycol diethyl ether diamine tetraacetic acid (mass ratio 2:3) 2 parts.

[0033] The breathable and antibacterial material is three-dimensional flower-like zinc oxide loaded water droplet-like copper oxide, and the preparation method comprises the following steps: Step one: 0.1~0.5g of zinc acetate dihydrate was dissolved in a 0.5~1mol / L sodium hydroxide aqueous solution, and then zinc sheet was added. After ultrasonic treatment for 10~30 min, the mixture was moved into a stainless steel reaction kettle to obtain a milky white mixed solution; Step two: the milky white solution prepared in step one was placed in an oven at 50~80℃, and then fully hydrothermally reacted for 24~48h until the reaction was complete. The zinc sheet was repeatedly washed with deionized water and ethanol for 3~5 times, and then dried in an oven at 50~80℃ to obtain three-dimensional flower-like zinc oxide; Step three: weigh copper acetate and sodium tetraborate decahydrate (molar ratio 1:5~10) and respectively dissolved in deionized water, ultrasonic dispersion to obtain a mixture of copper acetate-sodium borate solution, slowly add cocamide propyl betaine (molar ratio of cocamide propyl betaine and copper acetate is 1:50) under magnetic stirring, fully reacted for 30~60min, then add the three-dimensional flower-like zinc oxide prepared in step two, to obtain a blue mixed solution; Step four: the blue mixed solution prepared in step three is moved into the reaction kettle, and the reaction is carried out in the electric heating constant temperature air drying oven, the reaction temperature is 200℃, the reaction time is 12h, after reaction, natural cooling to room temperature, centrifugation, washing with deionized water and anhydrous ethanol alternately for three times, precipitating to the vacuum drying oven at 60℃ for 5h, finally obtaining three-dimensional flower-like zinc oxide loaded water droplet-like copper oxide.

[0034] The preparation method of the antibacterial and breathable midsole foaming material comprises the following steps: Step one: the base resin, breathable and antibacterial material, lubricant, crosslinking agent, blending agent are added into the high-speed mixer in sequence according to the weight fraction, and high-speed mixing is carried out to obtain a premix; Step two: the premix obtained in step one is added into the double screw extruder, and the processes of injecting supercritical CO2, shearing and mixing, pressure reduction extrusion, temperature rising foaming, cooling and shaping are carried out to obtain the antibacterial and breathable midsole foaming material. Comparative example 2

[0035] A high-resilience midsole foaming material and a preparation method thereof, comprising the following components by weight fraction: EVA resin 30 parts; TPEE resin 30 parts; high-resilience material 10 parts; zinc stearate 1 part; dicumyl peroxide 1 part; 2-oxopropandioic acid diethyl ester and ethylene glycol diethyl ether diamine tetraacetic acid (mass ratio 2:3) 2 parts.

[0036] The high-resilience material is a polymer high-elasticity microsphere, and the preparation method thereof comprises the following steps: Step one: weigh 150~300g of polyvinyl alcohol aqueous solution, add 2~5g of sodium pyrophosphate, and magnetically stir for 30~60min until dissolved uniformly, then place in a constant temperature cold bath pot to obtain solution A for standby; Step two: respectively weigh 2~5g of aminopropylmethylsiloxane-dimethylsiloxane copolymer and dissolve in 5~20mL of dichloromethane; 1~3g of dialdehyde-terminated polydimethylsiloxane is dissolved in 2~10mL of tetrahydrofuran, and the above two polysiloxane solutions are mixed uniformly to obtain solution B; Step three: slowly add solution B into solution A, emulsify for 10-30 min at a stirring rate of 300-500 / min, then raise the temperature to 50-80℃ and react for 3-6 h, centrifuge the emulsion at high speed, wash the upper layer of microspheres with deionized water, clean with ethanol and centrifuge for 3-6 times, and finally dry for 12-24 h to obtain the polymer high-elasticity microspheres, which are tested to have an average particle size ranging from 150 nm to 400 nm.

[0037] The preparation method of the high-resilience midsole foaming material comprises the following steps: Step one: add the base resin, high-resilience material, lubricant, crosslinking agent and blending agent into a high-speed mixer in sequence according to the weight fraction, and mix at high speed to obtain a premix; Step two: add the premix obtained in step one into a double-screw extruder, and perform processes such as supercritical CO2 injection, shear mixing, pressure reduction extrusion, temperature increase foaming, and cooling shaping to obtain the high-resilience midsole foaming material. Comparative example 3

[0038] A midsole foaming material and a preparation method thereof comprise the following components in terms of weight fraction: 30 parts of EVA resin, 30 parts of TPEE resin, 1 part of zinc stearate, 1 part of dicumyl peroxide, 2 parts of diethyl 2-oxalylmalonate and ethyleneglycol diethyl ether diaminetetraacetic acid (mass ratio of 2:3).

[0039] The preparation method of the midsole foaming material comprises the following steps: Step one: add the base resin, lubricant, crosslinking agent and blending agent into a high-speed mixer in sequence according to the weight fraction, and mix at high speed to obtain a premix; Step two: add the premix obtained in step one into a double-screw extruder, and perform processes such as supercritical CO2 injection, shear mixing, pressure reduction extrusion, temperature increase foaming, and cooling shaping to obtain the midsole foaming material.

[0040] Performance detection and result evaluation The samples prepared in examples 1-4 and comparative examples 1-3 above are tested: Test 1 Antibacterial test: accurately take 0.1 g of the sample and add it into a triangular flask containing 99 mL of sterile water, and use ultrasonic wave for 20 min. Add 1 mL of 10 7CFU / mL bacterial suspension. Another flask containing 99 mL of sterile water was taken as a blank control, and only 1 mL of bacterial suspension was added. The above flasks were placed in a shaking incubator and shaken at 37°C, 200 r / min for 30 min. 0.2 mL of the mixed solution was taken from each flask, appropriately diluted, and plated on a culture dish, which was incubated at 35°C for 48-72 h for colony counting. Each of the above two groups of samples was tested in triplicate, and the antibacterial rate was calculated according to the following formula: R = [(A-B) / A] * 100% R - antibacterial rate; A - average number of colonies of the blank control group; B - average number of colonies of the sample to be tested; The strains selected were Staphylococcus aureus and Escherichia coli.

[0041] Test 2 Rebound performance test: The rebound rates of the above examples and comparative examples were tested according to GB / T 6670-2008 "Soft Foam Polymeric Materials - Determination of Rebound Performance by Ball Drop Method", and the air permeability was tested according to GB / T 5453-1997 "Textile Fabric - Determination of Air Permeability", and the test results are shown in Tables 1-2: Table 1: Bacteriostatic performance test Sample Staphylococcus aureus (%) Escherichia coli (%) Example 1 99 98.5 Example 2 96 96 Example 3 99 97 Example 4 98 97 Comparative Example 1 99 97 Comparative Example 2 -- -- Comparative Example 3 -- -- Table 2: Rebound and air permeability performance test Sample Rebound rate (%) Air permeability (mL / cm2-h) Example 1 84 8820 Example 2 86 7035 Example 3 87 8653 Example 4 86 7313 Comparative Example 1 73 8787 Comparative Example 2 88 2476 Comparative Example 3 72 2515 As can be seen from the results of Tables 1-2, the self-made polymer high-elasticity microspheres are used as high-rebound materials in Examples 1-4, and the self-made three-dimensional flower-shaped zinc oxide loaded water-drop-shaped copper oxide is used as air-permeable and bacteriostatic material, which can significantly improve the rebound performance and air-permeable and bacteriostatic performance of the foaming material, and achieve long-acting air-permeable and bacteriostatic effect of the foaming material. This is because the special microsphere structure of the polymer high-elasticity microspheres and the special three-dimensional structure and water-drop shape of the three-dimensional flower-shaped zinc oxide loaded water-drop-shaped copper oxide can significantly improve the high-elasticity and air-permeable and bacteriostatic performance of the material.

[0042] The above only describes the preferred embodiments of the present application, and the protection scope of the present application is not limited to the above examples. Any technical solutions falling within the concept of the present application shall fall within the protection scope of the present application. It should be noted that, for ordinary skilled persons in the art, some improvements and refinements without departing from the principles of the present application shall also be considered as the protection scope of the present application.

Claims

1. A high-rebound, antimicrobial, and breathable midsole foamed material and a method for preparing the same, characterized by, It is prepared from the following raw materials by weight: 50~80 parts of base resin; 5~15 parts of high resilience material; 5~10 parts of breathable and bacteriostatic material; 0.5~1.5 parts of lubricant; 0.5~2 parts of crosslinking agent; 1~5 parts of blending agent; The base resin is at least two of EVA, POE, TPEE and TPE; The high resilience material is polymer high elasticity microspheres, and its preparation method comprises the following steps: Step one: weigh 150~300g of polyvinyl alcohol aqueous solution, add 2~5g of sodium pyrophosphate, and magnetically stir for 30~60min until dissolved uniformly, then place in a constant temperature cold bath pot to obtain solution A for standby; Step two: respectively weigh 2~5g of aminopropylmethylsiloxane-dimethylsiloxane copolymer and dissolve in 5~20mL of dichloromethane; 1~3g of dialdehyde-terminated polydimethylsiloxane is dissolved in 2~10mL of tetrahydrofuran, and the above two polysiloxane solutions are mixed uniformly to obtain solution B; Step three: slowly add solution B to solution A, emulsify at a stirring speed of 300~500 / min for 10~30min, then heat to 50~80℃ and react for 3~6h, then centrifuge the emulsion, wash the upper microspheres with deionized water, ethanol and centrifuge for 3~6 times, and finally dry for 12~24h to obtain polymer high elasticity microspheres, which are tested to have an average particle size range of 150~400nm; The breathable and bacteriostatic material is three-dimensional flower-shaped zinc oxide loaded with water droplet-shaped copper oxide, and its preparation method comprises the following steps: Step one: weigh 0.1~0.5g of zinc acetate dihydrate and dissolve in a 0.5~1mol / L sodium hydroxide aqueous solution, add zinc sheet, ultrasonic treat for 10~30min, then move to a stainless steel reaction kettle to obtain a milky white mixed solution; Step two: place the milky white solution obtained in step one in an oven at 50~80℃, and fully hydrothermally react for 24~48h until the reaction is complete, take out the zinc sheet, and repeatedly rinse with deionized water and ethanol for 3~5 times, then dry in an oven at 50~80℃ to obtain three-dimensional flower-shaped zinc oxide; Step three: weigh copper acetate and sodium tetraborate decahydrate (molar ratio 1:5~10) and dissolve in deionized water respectively, ultrasonic disperse uniformly to obtain a copper acetate-sodium borate mixed solution, slowly add amphoteric surfactant while magnetically stirring, fully react for 30~60min, then add the three-dimensional flower-shaped zinc oxide obtained in step two to obtain a blue mixed solution; Step four: move the blue mixed solution obtained in step three into a reaction kettle, react in an electric heating constant temperature air drying oven, naturally cool to room temperature after reaction, centrifuge the product, wash with deionized water and anhydrous ethanol alternately for three times, precipitate in a vacuum drying oven at 60℃ for 5h, and finally obtain three-dimensional flower-shaped zinc oxide loaded with water droplet-shaped copper oxide; The amphoteric surfactant in step three is at least one of cocamidopropylamine oxide, lauramidopropylamine oxide and dodecyl ethyloxy sulfobetaine, and the molar ratio of surfactant to copper acetate is 1:(50~100). The reaction temperature in the reactor in step four is 150-220 DEG C, and the reaction time is 10-20 h; The lubricant is at least one of stearic acid, zinc stearate and EVA wax; The crosslinking agent is dicumyl peroxide; The complexing agent is diethyl 2-oxopropandioate and ethylene glycol diethyl ether diamine tetraacetic acid with a mass ratio of 2:3-5.

2. A method for preparing a high-resilience, antibacterial, and breathable midsole foam material as described in claim 1, characterized in that, The method comprises the following steps: Step one: sequentially add base resin, high resilience material, air-permeable and antibacterial material, lubricant, crosslinking agent, complexing agent into a high-speed mixer according to weight fraction, and high-speed mix to obtain premix; Step two: add the premix obtained in step one into a double-screw extruder, and go through the processes of injecting supercritical CO2, shearing and mixing, pressure reduction and extrusion, temperature increase and foaming, and cooling and shaping to obtain air-permeable and antibacterial high resilience midsole foaming material.