High-elastic wear-resistant shoe sole material and preparation method thereof

Abstract

The application relates to the field of high polymer materials, and particularly discloses a high-elastic wear-resistant shoe sole material and a preparation method thereof. The high-elastic wear-resistant shoe sole material comprises the following raw materials in parts by weight: 40-85 parts of an EVA composition, 10-15 parts of EPDM, 10-15 parts of POE, 5-15 parts of a filler, 0.1-0.5 parts of stearic acid, 0.5-1 part of zinc stearate, 1-2 parts of zinc oxide, 0.5-1 part of a bridging aid, 1-2 parts of a foaming agent, 0.5-1 part of a crosslinking agent, 0.2-0.6 parts of a coupling agent, 5-20 parts of aminated silica-modified carbon nanotubes, and the aminated silica-modified carbon nanotubes comprise carboxyl carbon nanotubes and aminated silica in a mass ratio of 0.5-1:5.5. The shoe sole material has the advantages of high elastic recovery rate, good wear resistance, small compression permanent deformation and the ability to remove peculiar smell generated when the shoes are worn.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, and more particularly to a high-elastic wear-resistant shoe sole material and a preparation method thereof. BACKGROUND

[0002] The main materials for shoe soles are natural rubber or synthetic rubber, and the synthetic rubber is further divided into wear-resistant rubber, environment-friendly rubber, air rubber, adhesive rubber, hard rubber, carbon-added rubber, etc. The shoe soles made of these materials have different advantages. The natural rubber is very soft and has excellent elasticity, and can be suitable for various sports, but its resources are limited, harmful substances are generated in the production process, and it is not wear-resistant. The synthetic rubber (also called thermoplastic elastomer) has the advantages of simple processing method and process, but the air wear resistance, aging resistance and heat resistance are not ideal.

[0003] With the development of science and technology and the emergence of new materials, the performance of shoe materials has also been greatly improved. Ethylene-vinyl acetate copolymer (EVA) high-elastic foaming material has the characteristics of low density, good physical properties, excellent weather resistance, non-toxicity, etc., and has developed very rapidly in recent years and can be applied to the manufacture of high-grade sports shoes. However, the elasticity, tear resistance and peel resistance of the current EVA foaming material are not good enough, thereby limiting its use. For example, the characteristics of basketball, running and other sports require the shoe sole to have high elasticity (resilience greater than 50%), but most of the existing sports shoe soles are foaming materials blended with EVA and rubber, plastic elastomer, etc., and the elasticity is only 30-42%, which cannot meet the use requirements.

[0004] In the prior art, a high-elastic EVA shoe sole material is disclosed in Chinese Patent No. CN2014101576371, which includes the following components in weight parts: EVA7350 20-40 parts, EVA7470 30-50 parts, elastomer 5-15 parts, POE 5-15 parts, filler 5-15 parts, foaming agent 1-5 parts, coupling agent 0.2-0.6 parts, zinc oxide powder 0.5-1.5 parts, and stearic acid 0.1-0.5 parts. The elasticity of the EVA shoe sole material reaches more than 50%, which can meet the use requirements of high-elastic shoe soles. However, the inventors find that the high-elastic EVA shoe sole foaming material has a very large loss of resilience and a large permanent deformation after long-term wearing, and the mechanical properties are seriously reduced, and the wear resistance is poor, which seriously affects its application in the shoe material field. SUMMARY

[0005] In order to improve the elasticity and wear resistance of the shoe sole material, the present application provides a high-elastic wear-resistant shoe sole material and a preparation method thereof.

[0006] In the first aspect, the present application provides a high-elastic wear-resistant shoe sole material, which adopts the following technical scheme:

[0007] A high-elastic wear-resistant shoe sole material, comprising the following raw materials in parts by weight: 40-85 parts of EVA composition, 10-15 parts of EPDM, 10-15 parts of POE, 5-15 parts of filler, 0.1-0.5 parts of stearic acid, 0.5-1 parts of zinc stearate, 1-2 parts of zinc oxide, 0.5-1 parts of bridging aid, 1-2 parts of foaming agent, 0.5-1 parts of crosslinking agent, 0.2-0.6 parts of coupling agent, 5-20 parts of aminated silica modified carbon nanotubes, the aminated silica modified carbon nanotubes comprising carboxyl carbon nanotubes and aminated silica in a mass ratio of 0.5-1:5.5.

[0008] By adopting the above technical scheme, EVA is used as the main base material, and a certain amount of EPDM and POE is added. The POE copolymer has the characteristics of soft chain curling structure of octene and crystalline structure of ethylene chain, narrow relative molecular mass distribution, and uniform short branch chain distribution, so that it has good processability, fluidity, and excellent toughness. The elasticity of POE is relatively large, the molecular sequence distribution of POE is uniform, and POE has good compatibility with polyolefins. After POE is added to EVA, under the action of external impact force, a large number of crazes can be induced in the elastomer, and the matrix produces shear yielding. The composite foaming material mainly relies on crazes and shear bands to absorb energy, so that the tensile strength of the composite foaming material is improved, and the ability of the foaming material to store elastic deformation energy is also improved.

[0009] EPDM is a terpolymer of ethylene propylene rubber, which uses ethylene as the first monomer and propylene as the second monomer as raw materials, the main chain is completely saturated, the intermolecular cohesive energy is low, there is no large side group to hinder molecular movement, the molecular chain can maintain flexibility in a wide temperature range, and the unsaturated third monomer exists as a side group as a vulcanization active point. The unique molecular structure makes EPDM have excellent weather resistance, aging resistance, good elasticity, and small compression permanent deformation. POE and EPDM have good compatibility with EVA, and there is no obvious phase interface. The unsaturation of the molecular chain structure of the third monomer of EPDM makes it easy to crosslink, form a network of crosslinked elastomers, make the bubble pore diameter small, maintain a certain bubble internal pressure, and increase the wall thickness of the bubble wall. This can effectively prevent the collapse and damage of the bubble, and is beneficial to the recovery of the shape of the material.

[0010] The amino-silica modified carbon nanotube is made of amino-silica and acidified carbon nanotube, the carbon nanotube has unique nano structure and excellent mechanical, thermal and electrical properties, and is a reinforcing material for high-performance composite materials, but the carbon nanotube has large specific surface area and is easy to agglomerate due to the presence of van der Waals force, which leads to poor dispersibility of the carbon nanotube in the shoe sole material, affecting the reinforcing effect of the carbon nanotube, in addition, the surface of the carbon nanotube is chemically inert and lacks polar functional groups, and the compatibility of the carbon nanotube with the EVA composition and POE resin is poor, and an effective interface cannot be formed, while the amino-silica is grafted with amino groups on the surface after treatment, and the carbon nanotube is grafted with polar functional groups such as carboxyl and hydroxyl groups by mixed acid, the electronegativity of these polar functional groups is large, on the one hand, the electrostatic repulsion between the negatively charged carbon nanotubes is greater than the van der Waals force, which significantly improves the dispersibility of the carbon nanotube, on the other hand, the functional groups introduced on the surface of the carbon nanotube have good affinity with the polymer matrix, and good dispersion effect can be achieved; the amino groups on the surface of the silica and the carboxyl groups on the surface of the carbon nanotube will undergo dehydration reaction to form peptide bond, thereby grafting a certain thickness of silica on the surface of the carbon nanotube in the form of covalent bond, weakening the attraction between the carbon nanotubes, achieving the purpose of improving the dispersibility, and the amino-silica modified carbon nanotube uniformly dispersed in the resin matrix can achieve good reinforcing and wear-resistant effect.

[0011] Zinc stearate, zinc octadecanoate, chemical formula is formula C 36 H 70 O4Zn, which has excellent thermal stability and light stability, has bubble promoting effect for foamed products, and can help demolding due to its lubricating property, and zinc oxide helps foaming, the bridging agent is a transparent liquid which can effectively improve the bridging crosslinking efficiency of various polymers, increase the hardness and elongation, reduce the breaking elongation, and improve the compression.

[0012] Optionally, the EVA composition includes Thai Petrochemical UV1070 with a VA content of 40% and Yanshan Petrochemical 12J4 with a VA content of 12% in a mass ratio of 1:0.5-1.

[0013] By adopting the above technical scheme, the VA content affects the performance of EVA, a higher VA content makes the shoe sole material less rigid and less wear-resistant, and a lower VA content leads to a decrease in the elasticity and flexibility of the shoe sole material, therefore, the blended EVA composition with two different VA contents can obtain a shoe sole material with good resilience, strong compression deformation resistance and excellent wear resistance.

[0014] Optionally, the amino-silica modified carbon nanotube is pretreated as follows:

[0015] The PET and cellulose acetate are added into trifluoroacetic acid, and the carbon nanotube modified by aminosilica is added to modify the carbon nanotube, and the mixture is uniformly mixed to prepare a spinning solution, and the mass ratio of the PET, cellulose acetate and carbon nanotube modified by aminosilica in the spinning solution is 6-8:2-4:1.

[0016] The spinning solution is electrospun to prepare a spinning product, and the spinning product is cut into a fiber shape.

[0017] By adopting the above technical solution, the PET has good high-temperature resistance and hydrophobicity, the cellulose acetate has good thermal stability and spinning easy formability, the PET and cellulose acetate are electrospun by using a co-solvent to prepare a spinning product with nanofibers, the spinning product has a good fluffy structure, and the interpenetrating root-like fibers are locally hollow, thereby having good fluffiness and air filtration effect, the porosity of the spinning product is high, and the bulk density is low, so it is beneficial to the circulation and adsorption of gas, thereby improving the odor elimination effect of the shoe sole material, and the shoes do not produce odor even after being worn for a long time; the carbon nanotube modified by aminosilica is electrospun with the PET and cellulose acetate and cut into a fiber shape, the fiber-shaped carbon nanotube modified by aminosilica can be overlapped with each other in the shoe sole material, thereby improving the tensile strength and wear resistance of the shoe sole material and reducing the compression deformation rate.

[0018] Optionally, the spinning product is pretreated before being cut as follows:

[0019] The polyether ether ketone and a pore-forming agent are mixed and added into a mold; the spinning product is laid on the mixture of the polyether ether ketone and the pore-forming agent in the mold, and is pressurized to 1-2 MPa and heated to 380-390℃, and is kept for 3-5 min, and is washed and dried, and the thickness ratio of the spinning product to the mixture of the polyether ether ketone and the pore-forming agent is 1:0.1-0.2.

[0020] By adopting the above technical solution, the spinning product is laid on the mixture of the polyether ether ketone and the pore-forming agent, and is bonded with the polyether ether ketone after being heated and pressurized, and the polyether ether ketone has excellent mechanical comprehensive performance, good wear resistance and heat resistance, so that the polyether ether ketone bonded on the surface of the spinning product can further improve the tensile strength and wear resistance of the spinning product, and the pore-forming agent is also added, and the pore-forming agent is removed by washing with water to form pores on the polyether ether ketone, thereby improving the tensile strength and resilience of the polyether ether ketone, and the porous polyether ether ketone can further improve the gas adsorption property of the fiber-shaped carbon nanotube modified by aminosilica and improve the odor purification effect.

[0021] Optionally, the mass ratio of the polyether ether ketone to the pore-forming agent is 1:0.3-0.6.

[0022] By adopting the above technical scheme, the pore-forming agent can make the polyether ether ketone layer adhered to the surface of the spinning product have a porous structure, thereby improving the elasticity and tensile resistance of the polyether ether ketone, and making the polyether ether ketone have an adsorption effect and improving the odor elimination capability of the shoe sole material.

[0023] Optionally, the pore-forming agent is selected from at least one of sodium chloride, sucrose and PEG.

[0024] Optionally, after the mixture of the polyether ether ketone and the pore-forming agent is kept warm and pressurized, a solution of β-cyclodextrin in N,N-dimethylformamide with a concentration of 30-35 wt% is uniformly sprayed on the spinning product, and then dried, the spraying speed being 0.05-0.8 mm / min.

[0025] By adopting the above technical scheme, after the spinning product is adhered to the polyether ether ketone, a solution containing β-cyclodextrin is sprayed on the surface of the spinning product, and the β-cyclodextrin can effectively adsorb odor gas, thereby further improving the odor elimination effect of the shoe sole material.

[0026] Optionally, the filler is porous spherical silica.

[0027] By adopting the above technical scheme, the porous spherical silica has a special porous structure, and when mixed with a resin matrix such as EVA and EPDM, the resin matrix can be embedded in the porous structure, forming a matrix network that penetrates each other, thereby strengthening the interaction and bonding strength between the filler and the matrix, and improving the wear resistance of the shoe sole material.

[0028] Optionally, the crosslinking agent includes 1,4-bis-tert-butyl peroxyisopropyl benzene and triallyl isocyanurate with a mass ratio of 1:0.1-0.3.

[0029] By adopting the above technical scheme, 1,4-bis-tert-butyl peroxyisopropyl benzene is used as the main crosslinking agent, and triallyl isocyanurate is used as the crosslinking aid, so that the polymer molecular chains of EVA and the like are crosslinked to form a three-dimensional network structure, and the polymer has sufficient ability to constrain and wrap the gas generated by the decomposition of the foaming agent inside the polymer to form independent vesicles, thereby obtaining a shoe sole material with uniform foaming and good resilience.

[0030] In a second aspect, the application provides a preparation method of a high-elasticity and wear-resistant shoe sole material, which adopts the following technical scheme: a preparation method of a high-elasticity and wear-resistant shoe sole material, including the following steps:

[0031] Mixing the EVA composition, EPDM, POE, filler, stearic acid, zinc stearate, zinc oxide, coupling agent and amino-silica modified carbon nanotube, first-time closed kneading is carried out at 85-90℃, adding bridging aid, foaming agent and crosslinking agent, second-time closed kneading is carried out, and the material is turned over every 2-3min during the kneading to obtain the initial material;

[0032] Thinning the initial material at 65-85℃ to obtain the sheet material;

[0033] Granulating the sheet material to obtain the granular material, and the granulation temperature is 80-85℃;

[0034] Injection molding the granular material, and the injection molding temperature is 175-190℃, and the vulcanization time is 450-600s to obtain the high-elastic wear-resistant sole material.

[0035] Through the above technical scheme, the components are subjected to closed kneading, thinning, granulation and injection molding to obtain the sole material with good flexibility, good resilience and strong wear resistance.

[0036] In summary, the present application has the following beneficial effects:

[0037] 1. In the present application, the EVA composition is used as the matrix, POE and EPDM, and amino-silica modified carbon nanotube are added, POE and EPDM have good compatibility with the EVA composition, and can be uniformly dispersed with each other, thereby improving the resilience and compression permanent deformation of the sole material, the amino group on the silica in the amino-silica modified carbon nanotube reacts with the carboxyl group on the carbon nanotube to form a peptide bond, thereby improving the dispersibility of the carbon nanotube and improving the uniformity of the carbon nanotube in the EVA composition and other resins, thereby improving the wear resistance of the sole material.

[0038] 2. In the present application, PET and cellulose acetate are preferably used as the main components of the spinning solution, and amino-silica modified carbon nanotube is added, and the spinning product with a specific fluffy structure is formed by electrospinning, and after cutting, the fibrous amino-silica modified carbon nanotube is added to the sole material, and the fibrous amino-silica modified carbon nanotube can be overlapped with each other to form a network structure, thereby improving the resilience, reducing the wear amount and improving the wear resistance.

[0039] 3. In the present application, polyether ether ketone and the spinning product are preferably bonded, a polyether ether ketone layer is formed on one side of the spinning product, thereby further improving the tensile property and wear resistance of the spinning product, the addition of the porogen can make the polyether ether ketone layer have a porous structure, thereby further improving the resilience of the polyether ether ketone layer and making it have an odor removal effect, and the β-cyclodextrin is easily sprayed on the spinning product, thereby further improving the odor adsorption effect. DETAILED DESCRIPTION

[0040] Preparation example of aminated silica-modified carbon nanotubes

[0041] Preparation Example 1: (1) 1g of carbon nanotubes were added to 300ml of mixed acid solution (the volume ratio of nitric acid to sulfuric acid was 1:3), heated to 80℃, ultrasonically dispersed for 1h, and centrifuged at 5000rpm for 10min; the supernatant was poured off, the remaining carbon nanotubes were redispersed in deionized water, ultrasonically treated for 10min, filtered, washed until neutral, and dried to prepare carboxylated carbon nanotubes. The carbon nanotubes were multi-walled carbon nanotubes with an outer diameter of 7-15nm, a length of 5-15μm, a purity of >97%, a ash content of less than 3wt%, and a specific surface area of ​​250-500m². 2 / g, selected from even the city's Nanoport Co., Ltd., model number MWNT-10;

[0042] (2) 20g of silica was vacuum dried at 110℃ for 6h, and 200ml of toluene solution of silane coupling agent KH550 with a concentration of 5wt% was added. Under nitrogen protection, the mixture was refluxed at 110℃ for 8h, filtered, and vacuum dried at 110℃ to obtain aminated silica with a silica particle size of 3000 mesh.

[0043] (3) Disperse 0.5g of carboxylated carbon nanotubes into 300ml of dimethylformamide, add 5.5g of aminated silica, 20g of N,N-dicyclohexylcarbodiimide and 1.5g of dimethylaminopyridine, stir and react for 24h under nitrogen protection, filter, wash with deionized water, and vacuum dry at 80℃ for 24h.

[0044] Preparation Example 2: (1) 2g of carbon nanotubes were added to 300ml of mixed acid solution (the volume ratio of nitric acid and sulfuric acid was 1:3), heated to 85℃, ultrasonically dispersed for 0.5h, and centrifuged at 5000rpm for 8min; the supernatant was poured off, the remaining carbon nanotubes were redispersed in deionized water, ultrasonically treated for 10min, filtered, washed until neutral, and dried to prepare carboxylated carbon nanotubes. The carbon nanotubes were multi-walled carbon nanotubes with an outer diameter of 7-15nm, a length of 5-15μm, a purity of >97%, a ash content of less than 3wt%, and a specific surface area of ​​250-500m². 2 / g, selected from even the city's Nanoport Co., Ltd., model number MWNT-10;

[0045] (2) 10g of silica was vacuum dried at 100℃ for 8h, and 100ml of toluene solution of silane coupling agent KH550 with a concentration of 4wt% was added. The mixture was refluxed at 115℃ for 8.5h under nitrogen protection, filtered, and vacuum dried at 115℃ to obtain aminated silica with a silica particle size of 3000 mesh.

[0046] (3) 1 g of carboxylated carbon nanotubes were dispersed in 350 ml of dimethylformamide, 5.5 g of aminosilica, 30 g of N,N-dicyclohexyl carbodiimide and 2 g of dimethylamino pyridine were added, and the reaction was stirred for 24 h under nitrogen protection, filtered, washed with deionized water, and vacuum dried at 80°C for 24 h to obtain aminosilica modified carbon nanotubes.

[0047] Preparation Example 3: The difference from Preparation Example 1 is that the following steps are further included:

[0048] (4) PET and cellulose acetate were added to trifluoroacetic acid, and the aminosilica modified carbon nanotubes prepared in step (3) were added and mixed uniformly to obtain a spinning solution with a mass fraction of 11%, and the mass ratio of PET, cellulose acetate and aminosilica modified carbon nanotubes in the spinning solution was 8:2:1, the Mw of PET was 31500, and the Mw of cellulose acetate was 35000;

[0049] (5) The prepared spinning solution was electrospun to obtain a spinning product, which was cut into a fibrous shape with a length of 12 mm and a width of 2 mm, the spinning voltage was 26 kv, the receiving distance was 16 cm, and the spinning speed was 0.08 mm / min.

[0050] Preparation Example 4: The difference from Preparation Example 1 is that the following steps are further included:

[0051] (4) PET and cellulose acetate were added to trifluoroacetic acid, and the aminosilica modified carbon nanotubes prepared in step (3) were added and mixed uniformly to obtain a spinning solution with a mass fraction of 11%, and the mass ratio of PET, cellulose acetate and aminosilica modified carbon nanotubes in the spinning solution was 6:4:1, the Mw of PET was 31500, and the Mw of cellulose acetate was 35000;

[0052] (5) The prepared spinning solution was electrospun to obtain a spinning product, which was cut into a fibrous shape with a length of 12 mm and a width of 2 mm, the spinning voltage was 26 kv, the receiving distance was 16 cm, and the spinning speed was 0.08 mm / min.

[0053] Preparation Example 5: The difference from Preparation Example 3 is that no cellulose acetate is added to the spinning solution.

[0054] Preparation Example 6: The difference from Preparation Example 3 is that no PET is added to the spinning solution.

[0055] Preparation Example 7: Different from Preparation Example 3, step (5) is specifically as follows: the prepared spinning solution is electrospun to obtain a spinning product, the spinning voltage is 26kv, the receiving distance is 16cm, and the spinning speed is 0.08mm / min; the polyether ether ketone and the pore-forming agent are mixed and added into a mold, the spinning product is laid on the mixture of the polyether ether ketone and the pore-forming agent in the mold, the ratio of the laying thickness of the spinning product to the thickness of the mixture of the polyether ether ketone and the pore-forming agent is 1:0.1, the laying thickness of the spinning product is 100μm, heating to 2MPa and increasing the temperature to 380℃, keeping the temperature and pressure for 3min, washing, drying, and then cutting into a fibrous shape with a length of 12mm and a width of 2mm, the mass ratio of the pore-forming agent to the polyether ether ketone is 0.6:1, the pore-forming agent is sodium chloride, the average particle size of the polyether ether ketone is 25μm, and the density is 1.35g / cm 3 , which is selected from Jilin Zhongyan High Plastic, and the model number is 330UPF.

[0056] Preparation Example 8: Different from Preparation Example 3, step (5) is specifically as follows: the prepared spinning solution is electrospun to obtain a spinning product, the spinning voltage is 26kv, the receiving distance is 16cm, and the spinning speed is 0.08mm / min; the polyether ether ketone and the pore-forming agent are mixed and added into a mold, the spinning product is laid on the mixture of the polyether ether ketone and the pore-forming agent in the mold, the ratio of the laying thickness of the spinning product to the thickness of the mixture of the polyether ether ketone and the pore-forming agent is 1:0.2, the laying thickness of the spinning product is 100μm, heating to 1MPa and increasing the temperature to 390℃, keeping the temperature and pressure for 5min, washing, drying, and then cutting into a fibrous shape with a length of 12mm and a width of 2mm, the mass ratio of the pore-forming agent to the polyether ether ketone is 0.3:1, the pore-forming agent is sodium chloride, the average particle size of the polyether ether ketone is 25μm, and the density is 1.35g / cm 3 , which is selected from Jilin Zhongyan High Plastic, and the model number is 330UPF.

[0057] Preparation Example 9: Different from Preparation Example 7, the ratio of the laying thickness of the spinning product to the thickness of the mixture of the polyether ether ketone and the pore-forming agent is 1:0.5.

[0058] Preparation Example 10: Different from Preparation Example 7, the mass ratio of the pore-forming agent to the polyether ether ketone is 0.1:1.

[0059] Preparation Example 11: Different from Preparation Example 7, after the mixture of the polyether ether ketone and the pore-forming agent and the spinning product are kept at temperature and pressure in step (5), the mixture is washed and dried, a N,N-dimethylformamide solution of β-cyclodextrin with a concentration of 35wt% is uniformly sprayed on the spinning product at a spraying speed of 0.05mm / min, and the spinning product is cut into a fibrous shape with a length of 12mm and a width of 2mm after drying.

[0060] Example

[0061] Example 1: A high-elastic wear-resistant shoe sole material, comprising the following raw materials by weight: 65 kg of EVA composition, 12 kg of EPDM, 12 kg of POE, 13 kg of filler, 0.3 kg of stearic acid, 0.8 kg of zinc stearate, 2 kg of zinc oxide, 0.6 kg of bridging aid, 1.5 kg of foaming agent, 0.7 kg of crosslinking agent, 0.4 kg of coupling agent, 15 kg of aminosilica modified carbon nanotube, wherein the EVA composition comprises a mass ratio of 1:1 of UV1070 from Thailand Petrochemical with a VA content of 40% and 12J4 from Yanshan Petrochemical with a VA content of 12%, the EPDM is selected from Dow Chemical, USA, model 3720, the POE is selected from Dow Chemical, USA, model 7447, the filler is porous spherical silica, selected from Jiangxi Liankai New Materials, model Silspher P23, 50 average particle size 3 μm, the bridging aid is trimethylolpropane trimethacrylate, model PL-400, the foaming agent is azodicarbonamide, the crosslinking agent comprises a mass ratio of 1:0.1 of 1,4-bis-tert-butyl peroxyisopropyl benzene and triallyl isocyanurate, the coupling agent is coupling agent KH550, and the aminosilica modified carbon nanotube is prepared according to Preparation Example 1.

[0062] The preparation method of the high-elastic wear-resistant shoe sole material described above, comprising the following steps:

[0063] S1, mixing the EVA composition, EPDM, POE, filler, stearic acid, zinc stearate, zinc oxide, coupling agent and aminosilica modified carbon nanotube, first-time banburying at 85℃ for 10 min, adding the bridging aid, foaming agent and crosslinking agent, second-time banburying at 110℃ for 4 min, and turning over every 3 min to obtain a preliminary material; S2, thinning the preliminary material twice at 65℃ to obtain a sheet material, and the sheet material has a thickness of 1.5 mm;

[0064] S3, granulating the sheet material to obtain a granular material with a particle size of 3 mm, the temperature of the die head I of the extrusion granulator is 80℃, the temperature of the die head II is 80℃, the temperature of the electric heating I section is 80℃, the temperature of the electric heating II section is 80℃, the temperature of the electric heating III section is 80℃, the temperature of the electric heating IV section is 80℃, and the cooling water temperature is 15℃;

[0065] S4, injection molding the granular material at an injection temperature of 175℃ and a vulcanization time of 450 s to obtain the high-elastic wear-resistant shoe sole material.

[0066] Example 2: A high-elastic wear-resistant shoe sole material, comprising the following raw materials by weight: 40 kg of EVA composition, 10 kg of EPDM, 10 kg of POE, 5 kg of filler, 0.1 kg of stearic acid, 0.5 kg of zinc stearate, 1.5 kg of zinc oxide, 0.5 kg of bridging aid, 1 kg of foaming agent, 0.5 kg of crosslinking agent, 0.2 kg of coupling agent, 5 kg of aminosilica modified carbon nanotube, wherein the EVA composition comprises UV1070 of Siam Cement with a VA content of 40% and 12J4 of Yanshan Petrochemical with a VA content of 12% at a mass ratio of 1:0.5, the EPDM is selected from Dow Chemical, model 3720, the POE is selected from Dow Chemical, model 7447, the filler is porous spherical silica, the bridging aid is trimethylolpropane trimethacrylate, the foaming agent is azodicarbonamide, the crosslinking agent comprises 1,4-bis-tert-butyl peroxyisopropyl benzene and triallyl isocyanurate at a mass ratio of 1:0.3, the coupling agent is coupling agent KH550, and the aminosilica modified carbon nanotube is prepared in Preparation Example 2.

[0067] The preparation method of the high-elastic wear-resistant shoe sole material described above, comprising the following steps:

[0068] S1, mixing the EVA composition, EPDM, POE, filler, stearic acid, zinc stearate, zinc oxide, coupling agent and aminosilica modified carbon nanotube, first-time banburying at 90℃ for 8 min, adding the bridging aid, foaming agent and crosslinking agent, second-time banburying at 120℃ for 3 min, and turning over every 2 min to obtain a preliminary material; S2, thinning the preliminary material twice at 85℃ to obtain a sheet material with a thickness of 1.5 mm;

[0069] S3, granulating the sheet material to obtain a granular material with a particle size of 3 mm, the temperature of the die head I of the extrusion granulator is 85℃, the temperature of the die head II is 85℃, the temperature of the electric heating I section is 85℃, the temperature of the electric heating II section is 85℃, the temperature of the electric heating III section is 85℃, the temperature of the electric heating IV section is 85℃, and the temperature of the cooling water is 15℃;

[0070] S4, injection molding the granular material at an injection temperature of 190℃ and a vulcanization time of 600s to obtain the high-elastic wear-resistant shoe sole material.

[0071] Example 3: A kind of high elastic wear-resistant shoe sole material, the difference from example 1 is that the raw material is as follows: a kind of high elastic wear-resistant shoe sole material, including the following weight of raw materials: 85kg EVA composition, 15kg EPDM, 15kg POE, 15kg filler, 0.5kg stearic acid, 1kg zinc stearate, 2kg zinc oxide, 1kg bridging aid, 2kg foaming agent, 1kg crosslinking agent, 0.6kg coupling agent, 20kg aminosilica modified carbon nanotube, wherein the EVA composition includes 1:0.8 of VA content 40% of Thailand Petrochemical UV1070 and VA content 12% of Yanshan Petrochemical 12J4 by mass ratio, EPDM is selected from American Dow, model is 3720, POE is selected from American Dow, model is 7447, the filler is porous spherical silica, the bridging aid is trimethylolpropane trimethylacrylate, the foaming agent is azodicarbonamide, the crosslinking agent includes 1:0.2 of 1,4-bis-tert-butyl peroxide isopropyl benzene and triallyl isocyanurate by mass ratio, the coupling agent is coupling agent KH550, and the aminosilica modified carbon nanotube is made by preparation example 1.

[0072] The preparation method of the high elastic wear-resistant shoe sole material described above, comprising the following steps:

[0073] S1, the EVA composition, EPDM, POE, filler, stearic acid, zinc stearate, zinc oxide, coupling agent and aminosilica modified carbon nanotube are mixed, the first time is mixed in 90 DEG C, and the mixing time is 8 min, the bridging aid, foaming agent and crosslinking agent are added, the second time is mixed in 120 DEG C, and the mixing time is 3 min, and the material is turned over every 2 min, to obtain the initial material;S2, the initial material is thinned twice at 85 DEG C to obtain the sheet material, and the thickness of the sheet material is 1.5 mm;

[0074] S3, the sheet material is granulated to obtain the granules with a particle size of 3 mm, the temperature of the head I of the extrusion granulator is 85 DEG C, the temperature of the head II is 85 DEG C, the temperature of the electric heating I section is 85 DEG C, the temperature of the electric heating II section is 85 DEG C, the temperature of the electric heating III section is 85 DEG C, the temperature of the electric heating IV section is 85 DEG C, and the temperature of the cooling water is 15 DEG C;

[0075] S4, the granules are injection molded, the injection molding temperature is 190 DEG C, the vulcanization time is 600 s, and the high elastic wear-resistant shoe sole material is prepared.

[0076] Example 4: A kind of high elastic wear-resistant shoe sole material, the difference from example 1 is that the EVA is all VA content 40% of Thailand Petrochemical UV1070.

[0077] Example 5: A kind of high elastic wear-resistant shoe sole material, the difference from example 1 is that the EVA is all VA content 12% of Yanshan Petrochemical 12J4.

[0078] Example 6: A high energy return, wear resistant shoe sole material, differing from Example 1 in that the aminosilica-modified carbon nanotubes are made according to Preparative Example 3.

[0079] Example 7: A high energy return, wear resistant shoe sole material, differing from Example 1 in that the aminosilica-modified carbon nanotubes are made according to Preparative Example 4.

[0080] Example 8: A high energy return, wear resistant shoe sole material, differing from Example 6 in that the aminosilica-modified carbon nanotubes are made according to Preparative Example 5.

[0081] Example 9: A high energy return, wear resistant shoe sole material, differing from Example 6 in that the aminosilica-modified carbon nanotubes are made according to Preparative Example 6.

[0082] Example 10: A high energy return, wear resistant shoe sole material, differing from Example 6 in that the aminosilica-modified carbon nanotubes are made according to Preparative Example 7.

[0083] Example 11: A high energy return, wear resistant shoe sole material, differing from Example 6 in that the aminosilica-modified carbon nanotubes are made according to Preparative Example 8.

[0084] Example 12: A high energy return, wear resistant shoe sole material, differing from Example 10 in that the aminosilica-modified carbon nanotubes are made according to Preparative Example 9.

[0085] Example 13: A high energy return, wear resistant shoe sole material, differing from Example 10 in that the aminosilica-modified carbon nanotubes are made according to Preparative Example 10.

[0086] Example 14: A high energy return, wear resistant shoe sole material, differing from Example 10 in that the aminosilica-modified carbon nanotubes are made according to Preparative Example 11.

[0087] Comparative Example

[0088] Comparative Example 1: A high energy return, wear resistant shoe sole material, differing from Example 1 in that no POE is added.

[0089] Comparative Example 2: A high energy return, wear resistant shoe sole material, differing from Example 1 in that no EPDM is added.

[0090] Comparative Example 3: A high energy return, wear resistant shoe sole material, differing from Example 1 in that an equivalent amount of carbon nanotubes is used in place of the aminosilica-modified carbon nanotubes.

[0091] Comparative Example 4: A high energy return, wear resistant shoe sole material, differing from Example 1 in that no aminosilica-modified carbon nanotubes are added.

[0092] Preparation method of a high-elasticity EVA shoe sole material, comprising the following steps:

[0093] ①The following raw materials in parts by weight were mixed and fed into a mixer: EVA7350 (product of Dongguan Kerry Plastic Raw Material Co., Ltd., 18% VA content) 20 parts, EVA7470 (product of Dongguan Kerry Plastic Raw Material Co., Ltd., 26% VA content) 30 parts, elastomer (product of Quanzhou Yuanjian Chemical Co., Ltd., thermoplastic elastomer 0005) 5 parts, POE (product of Dongguan Yin Yang Plastic Trade Co., Ltd.) 5 parts, filler (product of Dongguan Yin Yang Plastic Trade Co., Ltd., rubber filler) 5 parts, foaming agent (product of Shanghai Jeyu Trade Co., Ltd., EVA foaming agent) 1 part, coupling agent (product of Nanjing Xiangqian Chemical Co., Ltd., KH-570) 0.2 parts, zinc oxide powder (product of Guangzhou Tao Yi Trade Co., Ltd., indirect method 99.7% zinc oxide powder) 0.5 parts, stearic acid (product of Guangzhou Tianhe District Daguanzhiyi Chemical Industry, 1801 stearic acid) 0.1 parts; the mixing temperature was 105°C, the air pressure was 0.65 kg, the mixing time was 10 min, and the turning time was 6 times;

[0094] ②The mixture obtained by mixing was fed into an open mill for open mixing, and the temperature was controlled at 80°C during open mixing, 15 mm per time, 3 mm per time, and 1 mm per time;

[0095] ③During the granulation process, the temperature of the granulator was 80°C, and the cooling water was kept unobstructed;

[0096] ④After cooling for 12 hours after discharging, the mixture was fed into a foaming machine, and the mixture was foamed in the foaming machine, the temperature of the foaming machine was 170°C, the pressure was 165 kg, and the time was 8 min;

[0097] ⑤The mixture was fed into an MD machine, the temperature of the MD machine was controlled at 180°C, the pressure was 90 kg, heating was performed for 400 seconds, and cooling was performed for 400 seconds to obtain the high-elasticity EVA shoe sole material.

[0098] Performance detection test

[0099] The shoe sole material was prepared according to the method in the examples and comparative examples, and the performance of the shoe sole material was detected according to the following method, and the detection results are shown in Table 1.

[0100] 1. Compression permanent deformation: detected according to HG / T2876-2009 "Compression Deformation Test Method for Micro-porous Materials of Rubber and Plastic Shoes";

[0101] 2. Resilience: detected according to GB / T10652-2001 "Determination of Elasticity of High Polymer Porous Elastic Materials";

[0102] 3. Tensile strength: tested according to GB / T6344-2008 "Determination of tensile strength and elongation at break of flexible cellular polymeric materials";

[0103] 4. Akron abrasion: tested according to GB / T1689-2014 "Determination of abrasion resistance of vulcanized rubber (using an Akron abrasion tester)";

[0104] 5. Odor eliminating effect: the sole material prepared in the examples and comparative examples was made into sports shoes, 10 people were selected to wear each example and comparative example, the amount of exercise of the 10 people was similar every day, the number of days for the sports shoes to produce odor was counted from the first day of wearing, and the test result was the average value of the 10 people, the larger the value, the better the odor eliminating effect of the sole material.

[0105] Table 1

[0106]

[0107]

[0108] It can be seen from Examples 1-3 and the data in Table 1 that the sole material prepared by using the EVA composition, EPDM and POE, amino-silica modified carbon nanotubes and the like has small compression deformation, high resilience, low Akron abrasion, large tensile strength, and good wear resistance and resilience.

[0109] In Example 4, only EVA with a VA content of 40% was used, and compared with Example 1, the prepared sole material had good resilience, but poor compression permanent deformation resistance, and the wear resistance decreased. In Example 5, EVA with a VA content of 12% was used, and the prepared sole material had poor resilience, but the compression permanent deformation and wear resistance were enhanced, indicating that the addition of two EVA with different VA contents could cooperate with each other to improve the resilience and wear resistance of the sole material.

[0110] In Examples 6 and 7, the amino-silica modified carbon nanotubes prepared in Preparation Examples 3 and 4 were used, respectively, compared with Example 1, the resilience and wear resistance of the sole material prepared in Examples 6 and 7 were further increased, and the compression permanent deformation did not become larger because of the increase in resilience, in addition, the time for the sole material to produce odor after continuous wearing was increased after the sole material was made into sports shoes, indicating that the resilience of the sole material prepared in Examples 6 and 7 was further improved, the compression permanent deformation resistance was increased, and the effect of resisting odor production was enhanced.

[0111] In Examples 8 and 9, the amino-silica modified carbon nanotubes prepared in Preparation Examples 5 and 6 were used, respectively, and no cellulose acetate and PET was added in Preparation Examples 5 and 6, respectively, compared with Example 6, the resilience of the sole material prepared in Examples 8 and 9 was weakened.

[0112] Example 10 and Example 11 use the amino-silica modified carbon nanotubes prepared in Preparation Example 7 and Preparation Example 8, and compared with Preparation Example 3, the spun product is treated with polyether ether ketone and pore-forming agent, the fibrous amino-silica modified carbon nanotubes prepared by this way is added into the sole material, the wear resistance of the prepared sole material is better, the wear amount is reduced, and the odor resistance effect is improved, and the tensile strength is increased.

[0113] Example 12 uses the amino-silica modified carbon nanotubes prepared in Preparation Example 9, compared with Preparation Example 7, the laid thickness of polyether ether ketone and pore-forming agent is increased, and it can be seen that the resilience of the sole material is reduced compared with Example 10, which indicates that the adhesion thickness of polyether ether ketone on one side of the spun product is increased, which will affect the resilience of the spun product, and the tensile strength is weakened.

[0114] Example 13 uses the amino-silica modified carbon nanotubes prepared in Preparation Example 10, compared with Preparation Example 7, the amount of pore-forming agent is reduced, and it can be seen from Table 1 that the resilience of the sole material prepared in Example 13 is reduced, the wear resistance is weakened, the odor resistance ability is weakened, but the compression deformation rate is reduced, and the anti-deformation ability is increased.

[0115] In Example 14, the compound of polyether ether ketone and pore-forming agent after heat preservation and pressure preservation is also post-treated with the spun product, and a β-cyclodextrin solution is sprayed, and the odor resistance effect of the prepared sole material is improved.

[0116] Comparative Example 1 and Comparative Example 2 do not add POE, and Comparative Example 2 does not add EPDM, and the data in Table 1 shows that the wear resistance and resilience of the sole material prepared in Comparative Example 1 and Comparative Example 2 are reduced, and the tensile strength is poor.

[0117] Comparative Example 3 uses unmodified carbon nanotubes, and Comparative Example 4 does not add carbon nanotubes, and it can be known through comparison that although the addition of carbon nanotubes can improve the wear resistance of the sole material, the poor dispersibility leads to the decrease of the mechanical strength of the sole material.

[0118] Comparative Example 5 is a preparation method of high-elastic sole provided by the prior art, and the high-elastic sole material prepared has high resilience and high tensile strength, but the wear resistance is poor.

[0119] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A high energy return, wear resistant shoe sole material, characterized by, The raw materials include the following weight parts: 40-85 parts of EVA composition, 10-15 parts of EPDM, 10-15 parts of POE, 5-15 parts of filler, 0.1-0.5 parts of stearic acid, 0.5-1 part of zinc stearate, 1-2 parts of zinc oxide, 0.5-1 part of bridging aid, 1-2 parts of foaming agent, 0.5-1 part of crosslinking agent, 0.2-0.6 part of coupling agent, 5-20 parts of aminosilica modified carbon nanotube; The filler is porous spherical silica; The EVA composition includes Thailand Petrochemical UV1070 with a VA content of 40% and Yanshan Petrochemical 12J4 with a VA content of 12% at a mass ratio of 1:0.5-1; The aminosilica modified carbon nanotube includes carboxyl carbon nanotube and aminosilica at a mass ratio of 0.5-1:5.5; The aminosilica modified carbon nanotube is pretreated as follows: PET and cellulose acetate are added to trifluoroacetic acid, and the aminosilica modified carbon nanotube is added, and mixed uniformly to prepare a spinning solution, and the mass ratio of PET, cellulose acetate and aminosilica modified carbon nanotube in the spinning solution is 6-8:2-4:1; The spinning solution is electrospun to prepare a spinning product, and the spinning product is cut into a fibrous shape; The spinning product is pretreated as follows before cutting: Polyether ether ketone and a pore former are mixed and added to a mold, and the mass ratio of the polyether ether ketone and the pore former is 1:0.3-0.6; The spinning product is laid on the mixture of polyether ether ketone and pore former in the mold, and is pressurized to 1-2 MPa and heated to 380-390℃, and is kept at temperature and pressure for 3-5 min, and the ratio of the thickness of the spinning product to the thickness of the mixture of polyether ether ketone and pore former is 1:0.1-0.2; After the mixture of polyether ether ketone and pore former and the spinning product are kept at temperature and pressure, a N,N-dimethylformamide solution of β-cyclodextrin with a concentration of 30-35 wt% is uniformly sprayed on the spinning product, and is dried, and the spraying speed is 0.05-0.8 mm / min.

2. The high-elasticity, wear-resistant shoe sole material according to claim 1, characterized in that The pore former is selected from at least one of sodium chloride, sucrose and PEG.

3. The high-elasticity, wear-resistant shoe sole material according to claim 1, characterized in that, The crosslinking agent includes 1,4-bis-tert-butyl peroxyisopropyl benzene and triallyl isocyanurate at a mass ratio of 1:0.1-0.

3.

4. The method of making a high energy return, wear resistant shoe sole material according to any one of claims 1-3, characterized in that, The method includes the following steps: The EVA composition, EPDM, POE, filler, stearic acid, zinc stearate, zinc oxide, coupling agent and aminosilica modified carbon nanotube are mixed, and are subjected to first closed mixing at 85-90℃, and the bridging aid, foaming agent and crosslinking agent are added, and are subjected to second closed mixing, and the mixing is carried out with turning over every 2-3 min to obtain a preliminary material; The preliminary material is thinned at 65-85℃ to obtain a sheet material; The sheet material is granulated to obtain a granular material, and the granulation temperature is 80-85℃; The granular material is injection molded, the injection molding temperature is 175-190℃, and the vulcanization time is 450-600 s to prepare a high-elastic wear-resistant sole material.

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