Lightweight wear-resistant rubber sole and preparation method thereof

Abstract

The invention relates to the field of rubber materials, and particularly discloses a lightweight wear-resistant rubber sole and a preparation method thereof. The lightweight wear-resistant rubber sole comprises the following raw materials in parts by weight: 100 parts of main rubber, 30-40 parts of a reinforcing agent, 25-30 parts of a foaming agent, 20-25 parts of a foaming aid, 4.8-5.2 parts of a cross-linking agent, 1-3 parts of an accelerant, 2-3 parts of stearic acid, 4-5 parts of zinc stearate, 9-12 parts of a dispersing agent and 1-2.5 parts of an anti-aging agent, the reinforcing agent comprises coupling modified hollow mesoporous silica spheres; the main rubber is prepared from cis-1, 4-polybutadiene rubber, polystyrene-butadiene rubber and isoprene according to the mass ratio of 1 to (2.3 to 2.5) to (2 to 2.3). The rubber sole is small in density, high in rebound rate, lighter and more comfortable to wear, high in wear resistance and tear resistance, small in compression rebound rate and long in service life.

Description

Technical Field

[0001] The present application relates to the technical field of rubber materials, and more specifically, to a lightweight and wear-resistant rubber sole and a preparation method thereof. Background Art

[0002] With the continuous development of sole materials, comfort and lightness have become an important criterion for people to choose shoes and boots. Therefore, high elasticity and lightness have become the main direction of the current development of sole materials. At present, PU, ​​EVA and other materials are mostly used to make lightweight soles on the market. Although PU soles and EVA foam soles are light in weight, they have poor low temperature resistance, skid resistance and aging resistance. Rubber, as a traditional sole material, has good wear resistance and skid resistance, and has environmental adaptability such as high temperature resistance and low temperature resistance, but the specific gravity of rubber is 1-1.4g / cm 3 , an ordinary sole weighs about 200-300 grams, which makes the shoes very heavy to wear.

[0003] In the prior art, a Chinese invention patent application document with application number 2017105424969 discloses a rubber foam sole material, which includes: 30 to 50 parts by weight of a base material, 16.5 to 27.5 parts by weight of a reinforcing agent, 11.5 to 19 parts by weight of an antioxidant, 1.5 to 2.5 parts by weight of an antifogging agent, 2 to 8 parts by weight of an active agent, 1 to 1.5 parts by weight of a vulcanizing agent, 1 to 1.5 parts by weight of an accelerator and 4 to 5 parts by weight of a foaming agent.

[0004] The above sole materials use a combination of butadiene rubber, styrene butadiene rubber and high styrene rubber as the base material, and use azodicarbonamide as a foaming agent to make a rubber foam material. Although it can reduce the density of the sole material and improve the wearing comfort, its wear resistance is poor and there is a big gap compared with ordinary solid rubber, which makes the soles easy to wear during actual wear, seriously affecting the wearing life of the shoes. Summary of the invention

[0005] In order to resolve the contradiction between lightweight and durability of rubber soles and improve the lightweight and wear resistance of rubber soles at the same time, the present application provides a lightweight and wear-resistant rubber sole and a preparation method thereof.

[0006] In a first aspect, the present application provides a lightweight wear-resistant rubber sole, which adopts the following technical solution: A lightweight wear-resistant rubber sole comprises the following raw materials in parts by weight: 100 parts of main rubber, 30-40 parts of reinforcing agent, 25-30 parts of foaming agent, 20-25 parts of foaming aid, 4.8-5.2 parts of cross-linking agent, 1-3 parts of accelerator, 2-3 parts of stearic acid, 4-5 parts of zinc stearate, 9-12 parts of dispersant, and 1-2.5 parts of antioxidant; The reinforcing agent includes coupled modified hollow mesoporous silica spheres; The main rubber comprises cis-1,4-polybutadiene rubber, polystyrene-butadiene rubber and isoprene in a mass ratio of 1:2.3-2.5:2-2.3.

[0007] By adopting the above technical scheme, coupling-modified hollow mesoporous silica spheres are used as reinforcing agents. After coupling modification, the hollow mesoporous silica spheres can be evenly dispersed in the rubber material, and a wide space is created between the inside and outside of the microspheres, allowing macromolecular substances to enter and exit through the pores, and can produce good interface interactions with rubber molecular chains, thereby significantly improving the wear resistance of the rubber soles. The hollow mesoporous silica spheres have a medium-sized internal and mesoporous surface structure, a large specific surface area, and a small density. As a reinforcing agent and nucleating agent, they can improve the tensile strength, tear strength, creep resistance, and compression resistance of the sole material, and can also improve the appearance of the rubber sole, reduce the shrinkage rate of the product, and increase the rigidity and stiffness of the product. Moreover, with the help of the dispersant, the reinforcing agent surface adsorbs the rubber molecules to form a large number of hydrogen bonds, which restricts the free movement of the macromolecules, which is equivalent to increasing the crosslinking density. At the same time, the reinforcing agent also acts as a nucleating agent to form a more dense microstructure of the bubbles, so the tensile strength and hardness of the rubber sole are relatively high. Strong, small permanent deformation, so it can reduce the density of rubber soles and improve its mechanical properties such as tensile resistance and tear resistance. At the same time, isoprene, cis-1,4-polybutadiene rubber and polystyrene-butadiene rubber are used as the main rubber. Cis-1,4-polybutadiene rubber has good elasticity, excellent wear resistance and flexural resistance, large molecular chain flexibility, and low glass transition temperature. It can form larger bubbles during the foaming process, thereby reducing the density of rubber soles, but has poor processing performance and will have a cold flow tendency, affecting the stability of foaming and the uniformity of pore structure. Polystyrene-butadiene rubber is composed of polystyrene hard segments and polybutadiene soft segments, combining the elasticity of rubber and the processability of plastics. The soft segment provides good elasticity, and the polystyrene hard segment helps to maintain the shape and stability of the foamed rubber. Isoprene is a high-performance rubber with good elasticity and wear resistance. It has good elasticity and wear resistance. Under the coordinated action of foaming agent, foaming aid, cross-linking agent and other ingredients, the pore wall of the rubber sole is complete, and a rubber foamed sole with excellent performance can be obtained.

[0008] Optionally, the preparation method of the coupled modified hollow mesoporous silica spheres is as follows: Phenolic resin and ethanol are mixed in a mass ratio of 1:4-5, and stirred and dissolved at 40-50°C to obtain a PR ethanol solution; hollow mesoporous silica spheres are added to the PR ethanol solution, stirred for 14-16 hours, and spray-dried to obtain mesoporous microspheres; the mesoporous microspheres are dispersed in a coupling agent ethanol solution with a concentration of 0.5-1wt%, immersed at room temperature for 8-10 hours, filtered, washed, and dried to obtain coupled modified hollow mesoporous silica spheres.

[0009] By adopting the above technical scheme, phenolic resin is a synthetic thermosetting resin with good wear resistance and excellent heat resistance. Its high temperature resistance can reach 250°C. Even in the advertising environment, phenolic resin can maintain its structural integrity and dimensional stability. Therefore, the phenolic resin is dissolved and mixed with hollow mesoporous silica, and the blended liquid is atomized into small droplets by spray drying. The solvent evaporates rapidly and the phenolic resin solidifies. Since the phenolic resin solution has a certain viscosity and good wettability, during the spraying process, it effectively adheres to and coats the pores and surface mesopores of the hollow mesoporous silica balls, which protects the hollow mesoporous silica balls, enhances their compression resistance, reduces their compression deformation, improves the compression resilience of the rubber sole, and increases wear resistance and tear resistance.

[0010] Optionally, the amount of the hollow mesoporous silica spheres is 10-25% of the PR ethanol solution.

[0011] By adopting the above technical scheme, the amount of hollow mesoporous silica spheres and PR ethanol solution is controlled. During spray drying, the phenolic resin can be evenly filled and coated on the surface and inside the pores of the hollow mesoporous silica spheres, thereby protecting and supporting the hollow mesoporous silica spheres, enhancing the wear resistance of the rubber sole without affecting the density and resilience of the sole.

[0012] Optionally, during the spray drying, the air inlet temperature is 220-230°C, the air outlet temperature is 88-92°C, and the feed rate is 50-55 mL / min.

[0013] By adopting the above technical solution and controlling the temperature, pressure and flow rate during spray drying, the atomization degree of the liquid can be increased, the drying speed can be accelerated, the droplet size can be reduced, and the particles of the product can be made more uniform.

[0014] Optionally, 30-40 parts by weight of auxiliary materials are further added to the rubber sole material, and the auxiliary materials include ethylene octene copolymer and modified ultra-high molecular weight polyethylene fiber in a mass ratio of 1:0.5-0.8.

[0015] By adopting the above technical scheme, the side octyl groups in the molecular structure of ethylene octene copolymer (POE) can form connecting points, which play a connecting and buffering role between the components. The network structure formed by these connecting points can undergo a large deformation, so the elongation at break and the wear resistance of the sole material are increased; ultra-high molecular weight polyethylene fiber is a high-strength, high-modulus fiber with a higher molecular weight, higher crystallinity, and excellent wear-resistant properties. It also has the advantages of high strength, large modulus, good corrosion resistance and low density. It can effectively resist wear and friction, protect the sole from damage, and significantly improve the wear resistance and service life of the sole material.

[0016] Optionally, the preparation method of the modified ultra-high molecular weight polyethylene fiber is as follows: The intercalated halloysite is pretreated with a coupling agent to obtain a coupled modified intercalated halloysite, which is then mixed with ultra-high molecular weight polyethylene powder, kneaded at 190-200° C. for 15-20 minutes, hot pressed at 200-205° C. and 15-20 MPa for 8-10 minutes, and crushed to obtain a composite powder, wherein the mass of the coupled modified intercalated halloysite is 2-2.5wt% of the ultra-high molecular weight polyethylene powder; The carbon nanotubes and the composite powder are added to the epoxy resin emulsion, and a curing agent is added after stirring evenly, and the treatment liquid is obtained by stirring evenly. The treatment liquid is sprayed on the ultra-high molecular weight polyethylene fiber and dried. The mass ratio of the composite powder, the carbon nanotubes and the epoxy resin emulsion is 0.05-0.1:0.2-0.3:1, and the mass ratio of the treatment liquid to the ultra-high molecular weight polyethylene is 0.05-0.1:1.

[0017] However, due to its higher molecular weight and higher crystallinity, usually more than 80%, the ultra-high molecular weight polyethylene fiber has a smooth surface and is chemically inert, and has poor interfacial bonding with the rubber matrix. In addition, the melting point of ultra-high molecular weight polyethylene fiber is between 130-136°C, which is lower than the vulcanization temperature of the rubber material, so it is easy to melt and damage its own performance. By adopting the above technical solution, the silane-modified intercalated halloysite plays the role of a molecular bridge in the ultra-high molecular weight polyethylene powder, forming a bonding state of inorganic phase / silane coupling agent / organic phase, improving the interfacial interaction between halloysite and ultra-high molecular weight polyethylene powder, and firmly connecting the two together, while the filling in the ultra-high molecular weight polyethylene powder is more convenient. Halloysite in high molecular weight polyethylene powder can improve the tribological properties of ultra-high molecular weight polyethylene. Moreover, it has a small particle size, a strong surface atomic effect, and good bonding with ultra-high molecular weight polyethylene powder. It acts as a dispersing aid in ultra-high molecular weight polyethylene powder in the form of nanoparticles, increasing the dispersibility of ultra-high molecular weight polyethylene powder, helping to improve the surface roughness of ultra-high molecular weight polyethylene, improve the contact angle, increase hydrophobicity, and improve the dispersion effect of the composite powder in epoxy resin. Halloysite has good heat resistance and can limit the movement range of ultra-high molecular weight polyethylene molecular chain segments, thereby improving the heat resistance of ultra-high molecular weight polyethylene and increasing the thermal stability of ultra-high molecular weight polyethylene during rubber vulcanization.

[0018] Composite powders and carbon nanotubes made of silane-modified intercalated halloysite and ultra-high molecular weight polyethylene powder are used as surface roughening particles and surface bonding auxiliary agents, and after being mixed with epoxy resin solution, the carbon nanotubes and the composite powders are adhered to ultra-high molecular weight polyethylene fibers using epoxy resin emulsion, thereby increasing the roughness of the surface of the ultra-high molecular weight polyethylene fiber and improving the interfacial bonding force between the ultra-high molecular weight polyethylene fiber and the rubber matrix. In addition, the carbon nanotubes on the fiber surface have strong heat resistance, and together with the halloysite, they improve the heat resistance of the ultra-high molecular weight polyethylene fiber to prevent hot melting during vulcanization and loss of fiber morphology. At the same time, they can further improve the wear resistance of the fiber. In addition, the epoxy resin emulsion is cured on the surface of the ultra-high molecular weight polyethylene fiber. It is a thermosetting resin with strong heat resistance, which can also improve the heat resistance of the fiber and also increase the wear resistance.

[0019] Optionally, the coupled modified intercalated halloysite is prepared by intercalating halloysite with trishydroxymethylaminomethane and then modifying it with vinyltriethoxysilane.

[0020] By adopting the above technical scheme, halloysite not only has a natural nano hollow tubular structure, but also has multiple types of surface hydroxyl groups. By using trishydroxymethylaminomethane intercalation with multiple hydroxyl and amino functional groups, the surface modification expands the interlayer spacing, improves its dispersibility and prevents aggregation. Then, the silanol of vinyltriethoxysilane is used to undergo a condensation reaction with the hydroxyl on the halloysite, and grafting is performed on the surface of the halloysite to improve the dispersibility of the halloysite in ultra-high molecular weight polyethylene.

[0021] Optionally, the foaming agent comprises N,N'-dinitrosopentamethylenetetramine and azodicarbonamide in a mass ratio of 1:0.3-0.5.

[0022] By adopting the above technical solution, N,N'-dinitrosopentamethylenetetramine and azodicarbonamide can synergistically accelerate the foaming process, improve the foaming efficiency, shorten the production cycle, and significantly increase the elasticity of the product.

[0023] Optionally, the foaming aid comprises polyethylene glycol dimethacrylate and a silane coupling agent in a mass ratio of 1:0.1-0.3.

[0024] By adopting the above technical scheme, the foaming aid is a mixture of polyethylene glycol dimethacrylate and a silane coupling agent, the polyethylene glycol dimethacrylate can play a certain role in assisting cross-linking, and the silane coupling agent has the ability to react with the rubber and then combine with the reinforcing agent, thereby promoting the dispersion of the rubber system, while improving the crystallinity of the composite material, moderately reducing the elasticity of the rubber material, and reducing the shrinkage of the rubber material during foaming. At the same time, due to the presence of hydroxyl and ester groups, strong hydrogen bonds are formed with the reinforcing agent, thereby driving the reinforcing agent to be evenly dispersed in the rubber system. When the foaming gas of the system impacts, the foaming rate of the rubber is also constrained to a certain extent, reducing its resilience, and forming a slow foaming product.

[0025] Optionally, the accelerator is selected from at least one of accelerator DM, accelerator D, and accelerator M; The crosslinking agent is selected from at least one of di-tert-butyl peroxide isopropylbenzene, sulfur, diisopropylbenzene peroxide, 5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane and di(2,4-dichlorobenzoyl)peroxide; The antioxidant is selected from at least one of antioxidant RD, antioxidant A, antioxidant 4010NA and antioxidant D; The dispersant is selected from at least one of polyethylene glycol, glycerol, sodium tripolyphosphate and water glass.

[0026] By adopting the above technical solution, di-tert-butyl peroxide isopropylbenzene can generate free radicals, which chemically react with the positions in the rubber molecular chain where free radical cross-linking can occur, thereby improving the tensile strength, tear strength and compression resistance of the rubber sole.

[0027] Rubber dispersants can improve the plasticity and mechanical properties of rubber soles, make the rubber raw materials evenly dispersed, better integrate the raw materials, and make the cross-linking between components more complete.

[0028] In a second aspect, the present application provides a method for preparing a lightweight wear-resistant rubber sole, which adopts the following technical solution: A method for preparing a lightweight wear-resistant rubber sole comprises the following steps: The main rubber, auxiliary materials and dispersant are mixed, heated to 110-115°C and kneaded for 3-5 minutes, a foaming aid is added, and the kneading is continued for 3-5 minutes, and then stearic acid, zinc stearate, reinforcing agent and antioxidant are added. After kneading for 3-5 minutes, a foaming agent, a cross-linking agent and an accelerator are added, and the kneading is continued for 3-5 minutes, and the sheet is produced and granulated to obtain pellets, and the pellets are injection molded, and then vulcanized once to obtain a primary embryo; The embryo is placed in a closed environment, nitrogen is introduced, the air is exhausted for 3-5 minutes, the temperature is raised to 50-55°C, the pressure is 18-20MPa, the temperature and pressure are kept constant for 3.5-4 hours, and secondary vulcanization is performed after exhaust to obtain the rubber sole.

[0029] By adopting the above technical scheme, the main rubber and other raw materials are mixed, vulcanized after injection molding, and the primary embryo is obtained, and then supercritical foaming and secondary vulcanization are performed. The secondary vulcanization can promote the distance between the small holes in series generated during the primary vulcanization and supercritical foaming to be further shortened, forming a more perfect three-dimensional cross-linked structure, so that the pore size is large, the inner wall of the pore is thin, the foaming effect is good, the resilience and stretchability are good, and the dimensional stability is better when facing external stress.

[0030] In summary, this application has the following beneficial effects: 1. Since the present application adopts cis-1,4-polybutadiene rubber, polystyrene-butadiene rubber and isoprene in a specific dosage ratio as the main rubber, and uses coupled modified hollow mesoporous silica balls as a reinforcing agent, the three main rubber raw materials cooperate with each other to obtain a rubber foam material with low density, good resilience, strong wear resistance and tear resistance, and the hollow mesoporous silica balls have a large specific surface area and low density, which can improve the compression resistance, tensile resistance and creep resistance of the sole material. Under the action of coupling modification, dispersant, cross-linking agent, etc., the pores of the rubber material can be made more uniform and dense, with lower density, making it lighter and more comfortable to wear, while having strong wear resistance, being more durable and practical.

[0031] 2. In the present application, it is preferred to first use a phenolic resin ethanol solution to spray-dry the hollow mesoporous silica spheres, and then perform coupling agent modification. After spray drying, the phenolic resin can protect and support the hollow mesoporous silica spheres, reduce their compression damage rate, increase their compression stability, and improve the compression rebound rate of the rubber sole. At the same time, it does not affect the density of the rubber material and increases the tear resistance and wear resistance of the rubber material.

[0032] 3. In this application, POE and modified ultra-high molecular weight polyethylene fibers are preferably used as auxiliary materials, which can improve the tensile and tear resistance of the rubber sole. At the same time, carbon nanotubes and composite powders containing halloysite are used to modify the ultra-high molecular weight polyethylene fibers under the adhesion of epoxy resin emulsion to increase their heat resistance, reduce their hot melt loss, improve their thermal stability, and increase the wear resistance, tensile and tear resistance of the sole. DETAILED DESCRIPTION

[0033] The following examples further illustrate the present application in detail.

[0034] Preparation Example 1-6 of Coupling Modified Hollow Mesoporous Silica Spheres Preparation Example 1: (1) 20 g of phenolic resin and ethanol were mixed in a mass ratio of 1:5, and stirred and dissolved at 50° C. to prepare a PR ethanol solution. The phenolic resin was selected from Dongguan Jiamai Plastics, model PR-50590; (2) adding hollow mesoporous silica spheres to the PR ethanol solution, stirring for 16 h, and spray drying to obtain mesoporous microspheres, wherein the hollow mesoporous silica spheres are selected from Jiangsu Xianfeng Nanomaterials, the model number is 7440-21-3, the diameter is 400 nm, and the addition amount of the hollow mesoporous silica spheres is 25% of the PR ethanol solution. During spray drying, the inlet air temperature is 230 ° C, the outlet air temperature is 92 ° C, and the feed rate is 55 mL / min; (3) The mesoporous microspheres were dispersed in a 1 wt% KH550 coupling agent ethanol solution, immersed at room temperature for 10 h, filtered, washed with deionized water, and dried to obtain coupled modified hollow mesoporous silica spheres.

[0035] Preparation Example 2: (1) 20 g of phenolic resin and ethanol were mixed in a mass ratio of 1:4, and stirred and dissolved at 40° C. to prepare a PR ethanol solution. The phenolic resin was selected from Dongguan Jiamai Plastics, model PR-50590; (2) adding hollow mesoporous silica spheres to the PR ethanol solution, stirring for 14 h, and spray drying to obtain mesoporous microspheres, wherein the hollow mesoporous silica spheres are selected from Jiangsu Xianfeng Nanomaterials, the model number is 7440-21-3, the diameter is 400 nm, and the addition amount of the hollow mesoporous silica spheres is 10% of the PR ethanol solution. During spray drying, the inlet air temperature is 220°C, the outlet air temperature is 88°C, and the feed rate is 50 mL / min; (3) The mesoporous microspheres were dispersed in a 0.5 wt % KH550 coupling agent ethanol solution, immersed at room temperature for 8 h, filtered, washed with deionized water, and dried to obtain coupled modified hollow mesoporous silica spheres.

[0036] Preparation Example 3: The difference from Preparation Example 1 is that the addition amount of the hollow mesoporous silica microspheres is 40% of the PR ethanol solution.

[0037] Preparation Example 4: The difference from Preparation Example 1 is that the addition amount of hollow mesoporous silica microspheres is 5% of the PR ethanol solution.

[0038] Preparation Example 5: (1) 20 g of phenolic resin and ethanol were mixed in a mass ratio of 1:5, and stirred and dissolved at 50° C. to prepare a PR ethanol solution. The phenolic resin was selected from Dongguan Jiamai Plastics, model PR-50590; (2) adding hollow mesoporous silica spheres to the PR ethanol solution, stirring for 16 h, and drying with hot air at 80° C. for 24 h to obtain mesoporous microspheres, wherein the hollow mesoporous silica spheres are selected from Jiangsu Xianfeng Nanomaterials, with a model of 7440-21-3 and a diameter of 400 nm, and the addition amount of the hollow mesoporous silica spheres is 25% of the PR ethanol solution; (3) The mesoporous microspheres were dispersed in a 1 wt% KH550 coupling agent ethanol solution, immersed at room temperature for 10 h, filtered, washed with deionized water, and dried to obtain coupled modified hollow mesoporous silica spheres.

[0039] Preparation Example 6: The hollow mesoporous silica spheres were dispersed in a 1 wt% KH550 coupling agent ethanol solution, immersed at room temperature for 10 h, filtered, washed with deionized water, and dried to obtain coupled modified hollow mesoporous silica spheres.

[0040] Preparation Example 7-13 of Modified Ultra-High Molecular Weight Polyethylene Fiber Preparation Example 7: (1) 5 g of halloysite was added to 300 ml of deionized water to form a dispersion, 3 g of tris(hydroxymethyl)aminomethane was added, ultrasonicated at a power of 40 kHz for 20 min, allowed to stand for 24 h, centrifuged, washed with water, and freeze-dried to obtain intercalated halloysite, 3.5 g of intercalated halloysite, 350 ml of ethanol, 50 ml of deionized water, and 3.5 ml of vinyltriethoxysilane were mixed, cooled and refluxed at 80° C. for 4 h, the product was washed with alcohol twice, washed with water once, and freeze-dried for 48 h to obtain coupled modified intercalated halloysite; (2) mixing the coupled modified intercalated halloysite with 20 g of ultra-high molecular weight polyethylene powder, kneading at 200° C. for 20 min, molding with a flat vulcanizer, hot pressing at 205° C. and 15 MPa for 10 min, and crushing after demolding to obtain a composite powder, wherein the mass of the coupled modified intercalated halloysite is 2.5 wt % of the mass of the ultra-high molecular weight polyethylene powder, and the ultra-high molecular weight polyethylene powder is selected from Daehan Petrochemical, model U050; (3) Add carbon nanotubes and composite powder to 50g of epoxy resin emulsion, add curing agent after stirring, stir evenly to obtain treatment liquid, spray the treatment liquid evenly on ultra-high molecular weight polyethylene fiber, and dry. The mass ratio of composite powder, carbon nanotubes and epoxy resin emulsion is 0.1:0.3:1, the mass ratio of treatment liquid to ultra-high molecular weight polyethylene is 0.1:1, the epoxy resin emulsion is bisphenol A epoxy resin selected from Hansen, USA, model 6520-WH-53A, the curing agent is polyamide 650, the mass ratio of curing agent to epoxy resin emulsion is 1:1, and the carbon nanotubes are selected from Beijing Tanyang Technology, model NC7000.

[0041] Preparation Example 8: (1) 5 g of halloysite was added to 300 ml of deionized water to form a dispersion, 3 g of tris(hydroxymethyl)aminomethane was added, ultrasonicated at a power of 40 kHz for 20 min, allowed to stand for 24 h, centrifuged, washed with water, and freeze-dried to obtain intercalated halloysite, 3.5 g of intercalated halloysite, 350 ml of ethanol, 50 ml of deionized water, and 3.5 ml of vinyltriethoxysilane were mixed, cooled and refluxed at 80° C. for 4 h, the product was washed with alcohol twice, washed with water once, and freeze-dried for 48 h to obtain coupled modified intercalated halloysite; (2) mixing the coupled modified intercalated halloysite with 20 g of ultra-high molecular weight polyethylene powder, kneading at 190° C. for 15 min, molding with a flat vulcanizer, hot pressing at 200° C. and 20 MPa for 8 min, and crushing after demolding to obtain a composite powder, wherein the mass of the coupled modified intercalated halloysite is 2 wt % of the mass of the ultra-high molecular weight polyethylene powder, and the ultra-high molecular weight polyethylene powder is selected from Daehan Petrochemical, model U050; (3) Add carbon nanotubes and composite powder to 50g of epoxy resin emulsion, add curing agent after stirring, stir evenly to obtain treatment liquid, spray the treatment liquid evenly on ultra-high molecular weight polyethylene fiber, and dry. The mass ratio of composite powder, carbon nanotubes and epoxy resin emulsion is 0.05:0.2:1, the mass ratio of treatment liquid to ultra-high molecular weight polyethylene is 0.05:1, the epoxy resin emulsion is bisphenol A epoxy resin selected from Hansen, USA, model 6520-WH-53A, the curing agent is polyamide 650, the mass ratio of curing agent to epoxy resin emulsion is 1:1, and the carbon nanotubes are selected from Beijing Tanyang Technology, model NC7000.

[0042] Preparation Example 9: The difference from Preparation Example 7 is that no composite powder is added.

[0043] Preparation Example 10: The difference from Preparation Example 7 is that an equal amount of ultra-high molecular weight polyethylene powder is used to replace the composite powder, and the ultra-high molecular weight polyethylene powder is selected from Korea Petrochemical, model U050.

[0044] Preparation Example 11: The difference from Preparation Example 7 is that no carbon nanotubes are added.

[0045] Preparation Example 12: The difference from Preparation Example 7 is that no epoxy resin emulsion and curing agent are added, and an equal amount of deionized water is used to replace the epoxy resin emulsion.

[0046] Preparation Example 13: (1) 5 g of halloysite was added to 300 ml of deionized water to form a dispersion, 3 g of tris(hydroxymethyl)aminomethane was added, ultrasonicated at a power of 40 kHz for 20 min, allowed to stand for 24 h, centrifuged, washed with water, and freeze-dried to obtain intercalated halloysite, 3.5 g of intercalated halloysite, 350 ml of ethanol, 50 ml of deionized water, and 3.5 ml of vinyltriethoxysilane were mixed, cooled and refluxed at 80° C. for 4 h, the product was washed with alcohol twice, washed with water once, and freeze-dried for 48 h to obtain coupled modified intercalated halloysite; (2) Add coupling modified intercalated halloysite to 50g of epoxy resin emulsion, stir evenly, then add curing agent, stir evenly to obtain a treatment liquid, spray the treatment liquid evenly on the ultra-high molecular weight polyethylene fiber, and dry. The mass ratio of coupling modified intercalated halloysite to epoxy resin emulsion is 0.1:0.3:1, the mass ratio of treatment liquid to ultra-high molecular weight polyethylene is 0.1:1, the epoxy resin emulsion is bisphenol A epoxy resin selected from Hansen, USA, model 6520-WH-53A, the curing agent is polyamide 650, the mass ratio of curing agent to epoxy resin emulsion is 1:1, and carbon nanotubes are selected from Beijing Carbon Yang Technology, model NC7000. Example

[0047] Example 1: A lightweight wear-resistant rubber sole, the raw material dosage is shown in Table 1, wherein the main rubber comprises cis-1,4-polybutadiene rubber, polystyrene-butadiene rubber and isoprene in a mass ratio of 1:2.3:2.3, the cis-1,4-polybutadiene rubber is selected from Yanshan cis-butadiene, model BR9000, the polystyrene-butadiene rubber is selected from Jilin styrene-butadiene rubber, model SBR1502, and the isoprene model is SKI-3S The reinforcing agent is the coupled modified hollow mesoporous silica sphere prepared in Preparation Example 1, the foaming agent includes N,N'-dinitrosopentamethylenetetramine and azodicarbonamide in a mass ratio of 1:0.5, the foaming aid includes polyethylene glycol dimethacrylate and silane coupling agent KH550 in a mass ratio of 1:0.3, the crosslinking agent is di-tert-butyl peroxide isopropylbenzene, the accelerator is accelerator DM, the dispersant is sodium tripolyphosphate, and the antioxidant is antioxidant RD.

[0048] The method for preparing the lightweight wear-resistant rubber sole comprises the following steps: S1. Mix cis-1,4-polybutadiene rubber, polystyrene-butadiene rubber and isoprene to obtain a main rubber, add a dispersant and mix well, heat to 110°C and knead for 5 minutes, add a foaming aid, continue kneading for 3 minutes, then add stearic acid, zinc stearate, reinforcing agent and antioxidant, add a foaming agent, a cross-linking agent and an accelerator after kneading for 5 minutes, continue refining for 3 minutes, thin twice at 80°C, and then sheet out to obtain a sheet, granulate the sheet to obtain a pellet with a particle size of 4 mm, injection mold the pellet at 120°C, and then vulcanize once at 130°C and 10MPa for 10 minutes to obtain a primary embryo; S2. Place the embryo in a closed environment, introduce nitrogen, exhaust for 5 minutes, raise the temperature to 55°C, and the pressure to 20MPa, maintain constant temperature and pressure for 4 hours, and after exhaust, perform secondary vulcanization at 170°C and 10MPa for 20 minutes to obtain a rubber sole.

[0049] Table 1 Raw material dosage of lightweight wear-resistant rubber soles in Examples 1-4 Raw material / kg Example 1 Example 2 Example 3 Example 4 Main glue 100 100 100 100 Reinforcement agent 40 37 33 30 Foaming agent 30 28 26 25 Foaming aid 25 23 22 20 Crosslinking agent 5.2 5.0 4.9 4.8 Accelerator 3 2.5 2 1 Stearic acid 3 2.6 2.3 2 Zinc stearate 5 4.7 4.4 4.0 Dispersants 12 11 10 9 Antioxidant 2.5 2 1.5 1 Example 2: A lightweight and wear-resistant rubber sole, the raw material dosage is as shown in Table 1, wherein the main rubber comprises cis-1,4-polybutadiene rubber, polystyrene-butadiene rubber and isoprene in a mass ratio of 1:2.5:2, the cis-1,4-polybutadiene rubber is selected from Yanshan butadiene, model BR9000, the polystyrene-butadiene rubber is selected from Jilin styrene-butadiene rubber, model SBR1502, the isoprene model is SKI-3S, the reinforcing agent is the coupled modified hollow mesoporous silica spheres prepared in Preparation Example 2, the foaming agent comprises N,N'-dinitrosopentamethylenetetramine and azodicarbonamide in a mass ratio of 1:0.3, the foaming aid comprises polyethylene glycol dimethacrylate and silane coupling agent KH550 in a mass ratio of 1:0.1, the crosslinking agent is diisopropyl peroxide, the accelerator is accelerator D, the dispersant is glycerol, and the antioxidant is antioxidant A.

[0050] The method for preparing the lightweight wear-resistant rubber sole comprises the following steps: S1. Mix cis-1,4-polybutadiene rubber, polystyrene-butadiene rubber and isoprene to obtain a main rubber, add a dispersant and mix well, heat to 115°C and knead for 3 minutes, add a foaming aid, continue kneading for 5 minutes, then add stearic acid, zinc stearate, a reinforcing agent and an antioxidant, add a foaming agent, a cross-linking agent and an accelerator after kneading for 3 minutes, continue refining for 5 minutes, thin twice at 80°C, and then sheet out to obtain a sheet material, and make the sheet material into The pellets are pelletized to obtain pellets with a particle size of 4 mm, and the pellets are injection molded at 125°C, and then vulcanized at 140°C and 8 MPa for 8 minutes to obtain a primary embryo; S2, the primary embryo is placed in a closed environment, nitrogen is introduced, and the exhaust is carried out for 3 minutes, the temperature is raised to 50°C, the pressure is 18 MPa, and the constant temperature and pressure are maintained for 3.5 hours. After exhausting, secondary vulcanization is carried out at 175°C and 8 MPa for 15 minutes to obtain a rubber sole.

[0051] Example 3-4: A lightweight wear-resistant rubber sole, which is different from Example 1 in that the amounts of raw materials used are as shown in Table 1.

[0052] Example 5: A lightweight and wear-resistant rubber sole. The difference from Example 1 is that the coupled modified hollow mesoporous silica spheres are made from Preparation Example 3.

[0053] Example 6: A lightweight and wear-resistant rubber sole. The difference from Example 1 is that the coupled modified hollow mesoporous silica spheres are made from Preparation Example 4.

[0054] Example 7: A lightweight and wear-resistant rubber sole. The difference from Example 1 is that the coupled modified hollow mesoporous silica spheres are made from Preparation Example 5.

[0055] Example 8: A lightweight and wear-resistant rubber sole. The difference from Example 1 is that the coupled modified hollow mesoporous silica spheres are made from Preparation Example 6.

[0056] Example 9: A lightweight, wear-resistant rubber sole. The difference from Example 1 is that 40 kg of auxiliary materials are further added to the raw materials. The auxiliary materials are prepared by mixing ethylene octene copolymer and modified ultra-high molecular weight polyethylene fiber in a mass ratio of 1:0.8, melting at 130°C, and then granulating. The ethylene octene copolymer is selected from Exxon Chemical, model 9361, and the modified ultra-high molecular weight polyethylene fiber is prepared by Preparation Example 7. The difference in the preparation method is that the auxiliary materials are first mixed with the main rubber and the dispersant, and the rest of the methods are the same.

[0057] Example 10: A lightweight, wear-resistant rubber sole. The difference from Example 1 is that 30 kg of auxiliary materials are further added to the raw materials. The auxiliary materials are prepared by mixing ethylene octene copolymer and modified ultra-high molecular weight polyethylene fiber in a mass ratio of 1:0.5, melting at 130°C, and then granulating. The ethylene octene copolymer is selected from Exxon Chemical, model 9361, and the modified ultra-high molecular weight polyethylene fiber is prepared by Preparation Example 8. The preparation method is different in that the auxiliary materials are first mixed with the main rubber and the dispersant, and the rest of the methods are the same.

[0058] Example 11: A lightweight and wear-resistant rubber sole. The difference from Example 9 is that the modified ultra-high molecular weight polyethylene fiber is made from Preparation Example 9.

[0059] Example 12: A lightweight, wear-resistant rubber sole. The difference from Example 9 is that the modified ultra-high molecular weight polyethylene fiber is made from Preparation Example 10.

[0060] Example 13: A lightweight and wear-resistant rubber sole. The difference from Example 9 is that the modified ultra-high molecular weight polyethylene fiber is made from Preparation Example 11.

[0061] Example 14: A lightweight and wear-resistant rubber sole. The difference from Example 9 is that the modified ultra-high molecular weight polyethylene fiber is made from Preparation Example 12.

[0062] Example 15: A lightweight and wear-resistant rubber sole. The difference from Example 9 is that the modified ultra-high molecular weight polyethylene fiber is made from Preparation Example 13.

[0063] Example 16: A lightweight and wear-resistant rubber sole. The difference from Example 9 is that no modified ultra-high molecular weight polyethylene fiber is added, an equal amount of POE is used to replace the modified ultra-high molecular weight polyethylene fiber, and the ethylene octene copolymer is selected from Exxon Chemical, model 9361.

[0064] Comparative Example Comparative Example 1: A lightweight wear-resistant rubber sole, which differs from Example 1 in that an equal amount of talcum powder is used to replace the coupled modified hollow mesoporous silica spheres.

[0065] Comparative Example 2: A lightweight wear-resistant rubber sole, which differs from Example 1 in that an equal amount of isoprene is used to replace polystyrene-butadiene rubber.

[0066] Comparative Example 3: A lightweight wear-resistant rubber sole, which differs from Example 1 in that an equal amount of isoprene is used to replace cis-1,4-polybutadiene rubber.

[0067] Comparative Example 4: A lightweight wear-resistant rubber sole, which differs from Example 1 in that isoprene is not added.

[0068] Comparative Example 5: A lightweight and wear-resistant rubber sole. The difference from Example 1 is that the primary embryo is not foamed with nitrogen, and no secondary vulcanization is performed. That is, after injection molding, vulcanization is performed at 170°C and 10MPa for 20 minutes to obtain the rubber sole.

[0069] Performance testing The shoe sole materials prepared in the examples and comparative examples were subjected to the following performance tests, and the test results are recorded in Table 2.

[0070] 1. Density: Test in accordance with GB / T532-2008 "Determination of density of vulcanized rubber or thermoplastic rubber".

[0071] 2. Akron wear: Test the wear resistance of the sole according to GB / T "1689-2014 Determination of wear resistance of vulcanized rubber (using Akron abrasion tester)". The test temperature is 23±2℃ and the humidity is 50±10%.

[0072] 3. Compression deformation rate: The test conditions are 50℃ and 6h, and the test is carried out in accordance with HG / T2876-2009 "Compression deformation test method for microporous materials of rubber and plastic shoes"; 4. Rebound rate: Tested in accordance with HG / T4993-2016 "Test method for rebound resilience of microporous materials for shoes".

[0073] 5. Tear strength: The tear strength of the sample is measured in accordance with GB / T "529-2008 Determination of tear strength of vulcanized rubber or thermoplastic rubber (trouser-shaped, right-angled and crescent-shaped specimens)". The specimen is a trouser-shaped specimen.

[0074] Table 2 Performance test of lightweight wear-resistant rubber sole Combining Examples 1-4 and the data in Table 2, it can be seen that the rubber soles prepared in Examples 1-4 have low density, good resilience, low compression rebound rate, strong wear resistance, good dimensional stability, light weight, high wearing comfort and long service life.

[0075] In Example 5 and Example 6, the silane-modified hollow mesoporous spheres prepared in Preparation Example 3 and Preparation Example 4 were used respectively. Compared with Preparation Example 1, the amounts of hollow mesoporous silica microspheres and PR ethanol solution in Preparation Example 3 and Preparation Example 4 were changed. It can be seen that the wear resistance of the rubber sole in Example 5 is enhanced, the compression deformation rate is low, but the density is increased, and the rebound rate is deteriorated. In Example 6, the density of the sole does not change much, but the wear resistance decreases, the compression deformation increases, the dimensional stability decreases, and the tear resistance deteriorates.

[0076] In Example 7, the silane-modified hollow mesoporous spheres prepared in Preparation Example 5 were used. Compared with Preparation Example 1, the hollow mesoporous silica spheres were mixed with the PR ethanol solution and then hot air dried to prepare mesoporous microspheres. The density of the rubber sole prepared in this way was increased, the rebound rate was reduced, and the tear resistance was deteriorated.

[0077] Compared with Example 1, Example 8 uses the silane-modified hollow mesoporous spheres prepared in Preparation Example 6, wherein only the KHH550 ethanol solution is used to treat the hollow mesoporous silica spheres. It can be seen from the data in Table 2 that the density of the rubber sole prepared in Example 8 does not change much, but the wear amount increases significantly, and the resilience becomes worse, the compression deformation rate increases, the dimensional stability is poor, and the tear resistance decreases.

[0078] Compared with Example 1, Examples 9 and 10 further add POE and modified ultra-high molecular weight polyethylene fiber as auxiliary materials to the rubber soles. Although the density of the rubber soles is slightly increased, the wear rate is significantly reduced, and the tear resistance and resilience are increased, the compression deformation is reduced, and the deformation resistance is increased.

[0079] In Example 11, the modified ultra-high molecular weight polyethylene fiber prepared in Preparation Example 9 was used. Compared with Example 9, the composite powder made of silane-modified intercalated halloysite and ultra-high molecular weight polyethylene powder was not added. From the data in Table 2, it can be seen that the tear resistance of the rubber sole prepared in Example 11 decreased and the wear resistance decreased.

[0080] In Example 12, the modified ultra-high molecular weight polyethylene fiber prepared in Preparation Example 10 was used. Compared with Example 9, when only ultra-high molecular weight polyethylene powder was used, the tear resistance and resilience of the rubber sole were reduced, indicating that silane-modified intercalated halloysite can increase the heat resistance and wear resistance of the ultra-high molecular weight polyethylene powder to prevent it from hot melting during vulcanization and affecting the interfacial adhesion between the ultra-high molecular weight polyethylene fiber and the rubber molecules.

[0081] In Example 13, the modified ultra-high molecular weight polyethylene fiber prepared in Preparation Example 11 was used. Compared with Example 9, no carbon nanotubes were added, and the wear resistance of the rubber sole was reduced and the tear resistance was weakened.

[0082] Example 14 adopts the modified ultra-high molecular weight polyethylene fiber prepared in Preparation Example 12. Compared with Example 9, deionized water is used instead of the epoxy resin emulsion. Table 2 shows that the wear resistance of the rubber sole is weakened and the tear resistance is poor.

[0083] In Example 15, the modified ultra-high molecular weight polyethylene fiber prepared in Preparation Example 13 was used, to which ultra-high molecular weight polyethylene powder and carbon nanotubes were not added. Compared with Example 9, the wear resistance and tear resistance of the rubber sole decreased.

[0084] In Example 16, only POE is used as an auxiliary material. Table 2 shows that, compared with Example 9, the density of the rubber sole prepared in Example 16 is increased, the wear resistance is reduced, and the properties such as rebound resilience are reduced.

[0085] In Comparative Example 1, talcum powder is used as a reinforcing agent. Compared with Example 1, the density of the rubber sole prepared in Comparative Example 1 is increased, the wear resistance is weakened, and the tear resistance is deteriorated.

[0086] Compared with Example 1, isoprene was used as raw material replacement in Comparative Examples 2 and 3, respectively. The density of the rubber soles prepared in Comparative Examples 2 and 3 was increased, the tear strength was reduced, and the resilience was deteriorated.

[0087] In Comparative Example 4, no isoprene was added. Compared with Example 1, the density of the rubber sole increased, the resilience became worse, and the tear resistance decreased.

[0088] In Comparative Example 5, nitrogen was not used for supercritical foaming, and secondary vulcanization was not performed. It can be seen that various properties of the rubber sole prepared were reduced.

[0089] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A lightweight and wear-resistant rubber sole, It is characterized in that The invention comprises the following raw materials in parts by weight: 100 parts of main adhesive, 30-40 parts of reinforcing agent, 25-30 parts of foaming agent, 20-25 parts of foaming aid, 4.8-5.2 parts of crosslinking agent, 1-3 parts of accelerator, 2-3 parts of stearic acid, 4-5 parts of zinc stearate, 9-12 parts of dispersant, and 1-2.5 parts of antioxidant; The reinforcing agent includes coupled modified hollow mesoporous silica spheres; The main rubber comprises cis-1,4-polybutadiene rubber, polystyrene-butadiene rubber and isoprene in a mass ratio of 1:2.3-2.5:2-2.

3.

2. The lightweight wear-resistant rubber sole according to claim 1, Features: The preparation method of the coupled modified hollow mesoporous silica spheres is as follows: The phenolic resin and ethanol are mixed in a mass ratio of 1:4-5, and stirred and dissolved at 40-50° C. to prepare a PR ethanol solution; The hollow mesoporous silica spheres were added to the PR ethanol solution, stirred for 14-16 hours, and spray-dried to obtain mesoporous microspheres. The mesoporous microspheres are dispersed in a coupling agent ethanol solution with a concentration of 0.5-1 wt%, immersed at room temperature for 8-10 hours, filtered, washed and dried to obtain coupled modified hollow mesoporous silica spheres.

3. The lightweight wear-resistant rubber sole according to claim 2, Features: The amount of the hollow mesoporous silica spheres used is 10-25% of the PR ethanol solution.

4. The lightweight wear-resistant rubber sole according to claim 2, Features: During the spray drying, the air inlet temperature is 220-230°C, the air outlet temperature is 88-92°C, and the feed rate is 50-55 mL / min.

5. The lightweight wear-resistant rubber sole according to claim 1, Features: 30-40 parts by weight of auxiliary materials are also added to the rubber sole material, and the auxiliary materials include ethylene octene copolymer and modified ultra-high molecular weight polyethylene fiber in a mass ratio of 1:0.5-0.

8.

6. The lightweight wear-resistant rubber sole according to claim 5, Features: The preparation method of the modified ultra-high molecular weight polyethylene fiber is as follows: The intercalated halloysite is pretreated with a coupling agent to obtain a coupled modified intercalated halloysite, which is then mixed with ultra-high molecular weight polyethylene powder, kneaded at 190-200° C. for 15-20 minutes, hot pressed at 200-205° C. and 15-20 MPa for 8-10 minutes, and crushed to obtain a composite powder, wherein the mass of the coupled modified intercalated halloysite is 2-2.5wt% of the ultra-high molecular weight polyethylene powder; The carbon nanotubes and the composite powder are added to the epoxy resin emulsion, and a curing agent is added after stirring evenly, and the treatment liquid is obtained by stirring evenly. The treatment liquid is sprayed on the ultra-high molecular weight polyethylene fiber and dried. The mass ratio of the composite powder, the carbon nanotubes and the epoxy resin emulsion is 0.05-0.1:0.2-0.3:1, and the mass ratio of the treatment liquid to the ultra-high molecular weight polyethylene is 0.05-0.1:

1.

7. The lightweight wear-resistant rubber sole according to claim 1, Features: The foaming agent comprises N,N'-dinitrosopentamethylenetetramine and azodicarbonamide in a mass ratio of 1:0.3-0.

5.

8. The lightweight wear-resistant rubber sole according to claim 1, Features: The foaming aid comprises polyethylene glycol dimethacrylate and a silane coupling agent in a mass ratio of 1:0.1-0.

3.

9. The lightweight wear-resistant rubber sole according to claim 1, Features: The accelerator is selected from at least one of accelerator DM, accelerator D and accelerator M; The cross-linking agent is selected from at least one of di-tert-butyl peroxide isopropylbenzene, sulfur, diisopropylbenzene peroxide, 5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane and di(2,4-dichlorobenzoyl)peroxide; The antioxidant is selected from at least one of antioxidant RD, antioxidant A, antioxidant 4010NA and antioxidant D; The dispersant is selected from at least one of polyethylene glycol, glycerol, sodium tripolyphosphate and water glass.

10. A method for preparing the lightweight wear-resistant rubber sole according to any one of claims 1 to 9, Features: The following steps are involved: The main rubber, auxiliary materials and dispersant are mixed, heated to 110-115°C and kneaded for 3-5 minutes, a foaming aid is added, and the kneading is continued for 3-5 minutes, and then stearic acid, zinc stearate, reinforcing agent and antioxidant are added. After kneading for 3-5 minutes, a foaming agent, a cross-linking agent and an accelerator are added, and the kneading is continued for 3-5 minutes, and the sheet is produced and granulated to obtain pellets, and the pellets are injection molded, and then vulcanized once to obtain a primary embryo; The embryo is placed in a closed environment, nitrogen is introduced, the air is exhausted for 3-5 minutes, the temperature is raised to 50-55°C, the pressure is 18-20MPa, the temperature and pressure are kept constant for 3.5-4 hours, and secondary vulcanization is performed after exhaust to obtain the rubber sole.

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