High-elasticity and compression-resistant composite foam material, preparation method thereof, and sole

Abstract

The present application relates to the field of shoe material manufacturing technology, and more particularly relates to a high-elasticity, compression-resistant composite foam material, a preparation method thereof, and a sole. The composite foam material comprises ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, a foaming agent, an activating agent, a bridging agent, a coupling agent, and zinc oxide. The high-elasticity, compression-resistant composite foam material is based on aliphatic thermoplastic polyurethane composite elastomer and ethylene vinyl acetate copolymer as main matrix materials, and through physical mixing between the two, the characteristics of ethylene vinyl acetate copolymer are improved, making it easy to degrade, reducing environmental pollution, and polyborosiloxane is also added simultaneously, making the composite foam material soft and comfortable, with excellent cushioning and rebound performance, excellent wear resistance (far exceeding ordinary EVA foam material), and good recovery performance, thereby meeting the performance requirements of sports shoe soles and bringing lasting comfortable experience to consumers.

Description

Technical Field

[0001] The present application relates to the technical field of shoe material manufacturing, and in particular to a highly elastic and compression-resistant composite foam material, a preparation method thereof, and a shoe sole. Background Art

[0002] With the development of social economy and the improvement of people's living standards, people's awareness of scientific shoe wearing is constantly increasing, and light, comfortable and beautiful footwear products are becoming more and more popular. The sole material is a by-product of footwear products. With the development of footwear products, the quality of sole materials is constantly improving.

[0003] Commonly used materials for soles currently available on the market are PVC (polyvinyl chloride), PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), rubber, etc., all of which are petrochemical products. They are all polymers. Due to their high degree of polymerization and strong intermolecular forces, the polymer chains are difficult to break and decompose, resulting in the existing shoe materials and shock-resistant sheets for packaging being non-degradable and polluting the environment. The soles made from them are hard and dense, with poor cushioning and resilience. After wearing for a period of time, they will collapse and have poor resilience, seriously affecting the feel of athletes wearing sports shoes. Summary of the Invention

[0004] Other features and advantages of the present application will be described in the following description, and in part will become apparent from the description, or will be understood by practicing the present application. The purpose and other advantages of the present application can be realized and obtained through the structures specifically pointed out in the description and the drawings.

[0005] The present application aims to overcome the above-mentioned deficiencies and provide a highly elastic and compression-resistant composite foam material, a preparation method thereof, and a sole. The highly elastic and compression-resistant composite foam material uses an aliphatic thermoplastic polyurethane composite elastomer and an ethylene-vinyl acetate copolymer as main matrix materials, thereby reducing the amount of ethylene-vinyl acetate copolymer used and significantly reducing dependence on petrochemical raw materials, which is beneficial to environmental protection. Furthermore, the physical mixing of the polycaprolactone thermoplastic polyurethane elastomer and the ethylene-vinyl acetate copolymer improves the properties of the ethylene-vinyl acetate copolymer, making it easy to degrade and reducing environmental pollution. Furthermore, the addition of polyborosiloxane makes the composite foam material soft and comfortable, with excellent cushioning and rebound properties, excellent wear resistance (far exceeding that of ordinary EVA foam materials), and good recovery performance, thereby meeting the performance requirements of sports shoe soles and providing consumers with a lasting comfortable experience.

[0006] In a first aspect, the present application provides a highly elastic and compression-resistant composite foam material. The composite foam material comprises ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide;

[0007] Based on the total mass of the composite foam material,

[0008] The mass content of the ethylene vinyl acetate copolymer is 20.5%-33.5%, the mass content of the aliphatic thermoplastic polyurethane composite elastomer is 55%-60%, the mass content of the polyborosiloxane is 5%-10%, the mass content of the foaming agent is 2.5%-4%, the mass content of the active agent is 1%-2%, the mass content of the bridging agent is 0.7%-1.2%, the mass content of the coupling agent is 1.3%-1.8%, and the mass content of the zinc oxide is 1%-1.5%.

[0009] This application is mainly based on aliphatic thermoplastic polyurethane composite elastomer, supplemented by ethylene vinyl acetate copolymer, which reduces the use of ethylene vinyl acetate copolymer, greatly reduces dependence on petrochemical raw materials, is beneficial to environmental protection, and through the physical mixing of polycaprolactone thermoplastic polyurethane elastomer and ethylene vinyl acetate copolymer, improves the properties of ethylene vinyl acetate copolymer, making it easy to degrade and reducing environmental pollution. In addition, this application also adds polyborosiloxane, which, under the synergistic effect of the proportions of various components, greatly reduces the compression deformation and weight of the composite foam material, greatly improving the resilience of the composite foam material. The composite foam material is soft and comfortable, with excellent cushioning and rebound properties, and excellent wear resistance (far exceeding ordinary EVA foam materials), thereby meeting the performance requirements of sports shoe soles and providing consumers with a lasting comfortable experience.

[0010] In some embodiments, the aliphatic thermoplastic polyurethane composite elastomer includes polycaprolactone thermoplastic polyurethane elastomer, styrene-isoprene-butadiene hydrogenated copolymer, ethylene vinyl acetate copolymer, thermoplastic vulcanizate, and EPDM rubber;

[0011] Based on the total mass of the aliphatic thermoplastic polyurethane composite elastomer,

[0012] The mass content of the polycaprolactone thermoplastic polyurethane elastomer is 40%-45%, the mass content of the styrene-isoprene-butadiene hydrogenated copolymer is 15%-20%, the mass content of the ethylene vinyl acetate copolymer is 20%-38%, the mass content of the thermoplastic vulcanized rubber is 2%-5%, and the mass content of the EPDM rubber is 5%-10%.

[0013] The present application improves the properties of ethylene vinyl acetate copolymer by physically mixing polycaprolactone thermoplastic polyurethane elastomer with ethylene vinyl acetate copolymer, making it easy to degrade and reducing environmental pollution; at the same time, under the specific ratio of raw materials, the physical mixture is melt-blended with styrene-isoprene-butadiene copolymer hydrogenated polymer, thermoplastic vulcanizate and EPDM rubber to achieve a cross-linking reaction, thereby modifying the polycaprolactone, improving the strength and toughness, and lowering the melting point of the polycaprolactone thermoplastic polyurethane elastomer, so that it can be completely melt-blended with the ethylene vinyl acetate copolymer.

[0014] In some embodiments, the polyborosiloxane is formed by reacting polydimethylsiloxane with boric acid at 250°C-300°C. In polyborosiloxane, electron-deficient boron atoms gain electrons from electron-paired oxygen atoms in adjacent molecules, forming BO crosslinks. These crosslinks absorb thermal energy and break at room temperature, resulting in the composite foam material exhibiting deformation properties similar to those of Silly Putty when subjected to stress. Furthermore, when subjected to high-speed impact, the molecular structure forms a network, exhibiting shock absorption and high resilience, as the impact time is shorter than the thermal breakage time of the crosslinks.

[0015] In some embodiments, the mass ratio of the polydimethylsiloxane to the boric acid is 25:2-4. By rationally controlling the mass ratio of polydimethylsiloxane to boric acid, the present invention ensures that electron-deficient boron atoms acquire sufficient electrons from electron-paired oxygen atoms in adjacent molecules, thereby forming a sufficient number of BO cross-links. This allows the composite foam material to exhibit compression deformation properties when subjected to stress, and allows the molecules to form a sufficient network structure when subjected to high-speed impact, thereby exhibiting properties such as shock absorption and high resilience.

[0016] In some embodiments, the reaction time is 70 h to 74 h. By rationally controlling the reaction time of polydimethylsiloxane and boric acid, the present invention ensures that the electron-deficient boron atoms obtain sufficient electrons from the electron-paired oxygen atoms in the adjacent molecules, thereby forming sufficient BO cross-links, allowing the polyiodosiloxane to play a greater role.

[0017] In some embodiments, the ethylene-vinyl acetate copolymer has an acetic acid content of 28%. By physically blending an ethylene-vinyl acetate copolymer having an acetic acid content of 28% with a polycaprolactone thermoplastic polyurethane elastomer, the present application improves the properties of the ethylene-vinyl acetate copolymer, making it easier to degrade and reducing environmental pollution. Furthermore, the present application significantly improves the strength and toughness of the aliphatic thermoplastic polyurethane composite elastomer by using an ethylene-vinyl acetate copolymer having an acetic acid content of 28%, lowers the melting point of the polycaprolactone thermoplastic polyurethane elastomer, and enables complete melt blending with the ethylene-vinyl acetate copolymer.

[0018] In some embodiments, the ethylene-vinyl acetate copolymer includes an ethylene-vinyl acetate copolymer with an acetic acid content of 33% and an ethylene-vinyl acetate copolymer with an acetic acid content of 28%, wherein the weight ratio of the ethylene-vinyl acetate copolymer with an acetic acid content of 33% to the ethylene-vinyl acetate copolymer with an acetic acid content of 28% is 1:5-1:3. The present application, by reasonably selecting the weight ratio between the ethylene-vinyl acetate copolymer with an acetic acid content of 33% and the ethylene-vinyl acetate copolymer with an acetic acid content of 28%, and under the synergistic effect of the proportions of various components, greatly reduces the compression deformation and weight of the composite foam material, thereby greatly improving the resilience of the composite foam material. The composite foam material is soft and comfortable, has excellent cushioning and resilience properties, and is excellent in wear resistance (far exceeding that of ordinary EVA foam materials), thereby meeting the performance requirements of sports shoe soles and providing consumers with a lasting comfortable experience.

[0019] In a second aspect, the present application provides a method for preparing a highly elastic and compression-resistant composite foam material. The preparation method comprises the following steps:

[0020] In a primary mixing step, ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, active agent, bridging agent, and zinc oxide are placed at 120° C. to 150° C. and kneaded for 7 min to 10 min to form a first mixed material;

[0021] Secondary mixing: adding the foaming agent and coupling agent to the first mixture, and mixing at 130-140°C for 2-3 minutes to form a second mixture;

[0022] Granulation: placing the second mixed material at 80° C.-90° C. for granulation to form a composite material;

[0023] Foaming: placing the composite material at 160°C-170°C for foaming to form a highly elastic and compression-resistant composite foam material.

[0024] The present invention first blends ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, an active agent, a bridging agent, and zinc oxide and performs a primary banburying process. A blowing agent and a coupling agent are then added and blended, followed by a secondary banburying process. The mixture is then granulated and foamed to produce a highly elastic and compression-resistant composite foam material. The composite foam material is soft and comfortable, has excellent cushioning and rebound properties, is highly wear-resistant (far exceeding ordinary EVA foam materials), and exhibits good recovery properties, thereby meeting the performance requirements of sports shoe soles and providing consumers with a long-lasting, comfortable experience.

[0025] In some embodiments, the preparation method further comprises the step of preparing an aliphatic thermoplastic polyurethane composite elastomer, the preparation step being:

[0026] Adding polycaprolactone thermoplastic polyurethane elastomer, styrene-isoprene-butadiene copolymer hydrogenated polymer, ethylene vinyl acetate copolymer, thermoplastic vulcanized rubber, and ethylene propylene diene monomer rubber into a twin-screw extruder, blending and extruding to obtain an aliphatic thermoplastic polyurethane composite elastomer;

[0027] The blending time is 3 min to 5 min, and the blending temperature is 150° C. to 180° C.

[0028] The present application improves the properties of ethylene vinyl acetate copolymer by physically mixing polycaprolactone thermoplastic polyurethane elastomer with ethylene vinyl acetate copolymer, making it easy to degrade and reducing environmental pollution; at the same time, under the specific ratio of raw materials, the physical mixture is melt-blended with styrene-isoprene-butadiene copolymer hydrogenated polymer, thermoplastic vulcanizate and EPDM rubber to achieve a cross-linking reaction, thereby modifying the polycaprolactone, improving the strength and toughness, and lowering the melting point of the polycaprolactone thermoplastic polyurethane elastomer, so that it can be completely melt-blended with the ethylene vinyl acetate copolymer.

[0029] In some embodiments, the temperature of the twin-screw feeding zone of the twin-screw extruder is 100°C-120°C, and the temperature of the plasticizing zone is 130°C-150°C.

[0030] In some embodiments, the twin-screw head temperature of the twin-screw extruder is 90°C-110°C.

[0031] In some embodiments, the twin-screw speed of the twin-screw extruder is 20 rpm to 40 rpm.

[0032] In a third aspect, the present application provides a shoe sole. The shoe sole is made of a highly elastic and compression-resistant composite foam material that is foamed using a foaming mold, then heated, shaped, and cooled using a forming mold. The highly elastic and compression-resistant composite foam material includes ethylene-vinyl acetate copolymer, an aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide.

[0033] Based on the total mass of the composite foam material,

[0034] The mass content of the ethylene vinyl acetate copolymer is 20.5%-33.5%, the mass content of the aliphatic thermoplastic polyurethane composite elastomer is 55%-60%, the mass content of the polyborosiloxane is 5%-10%, the mass content of the foaming agent is 2.5%-4%, the mass content of the active agent is 1%-2%, the mass content of the bridging agent is 0.7%-1.2%, the mass content of the coupling agent is 1.3%-1.8%, and the mass content of the zinc oxide is 1%-1.5%.

[0035] The present application utilizes a highly elastic and compression-resistant composite foam material to be foamed, heated, shaped, and cooled to form a highly elastic and compression-resistant sole, thereby reducing the weight of a single sole by about 60%. At the same time, the density of a single sole is only about 40% of the density of a traditional sole. In addition, the sole is soft and comfortable, has excellent cushioning and rebound properties, is excellent in wear resistance (far exceeding ordinary EVA foam soles), and has good recovery performance, effectively solving the technical problem of the sole "becoming hard from soft and undergoing large permanent deformation" after long-term wear, greatly extending the service life of the sole, enhancing the durability of the sole, and improving the wearer's wearing experience.

[0036] In some embodiments, the foaming temperature is 160-180° C., and the foaming time is 400-600 seconds. The present application significantly improves the foaming ratio by reasonably controlling the foaming temperature and foaming time of the highly elastic and compression-resistant composite foam material in the foaming mold.

[0037] In some embodiments, the heating temperature is 165°C-185°C, the heating time is 500s-700s, and the shaping pressure is 80kg / m 2 -100kg / m 2 The present invention improves the structural stability of the sole by reasonably controlling parameters such as heating and shaping.

[0038] By adopting the above technical solution, the beneficial effects of this application are:

[0039] This application is mainly based on aliphatic thermoplastic polyurethane composite elastomer, supplemented by ethylene vinyl acetate copolymer, which reduces the use of ethylene vinyl acetate copolymer, greatly reduces dependence on petrochemical raw materials, is beneficial to environmental protection, and through the physical mixing of polycaprolactone thermoplastic polyurethane elastomer and ethylene vinyl acetate copolymer, improves the properties of ethylene vinyl acetate copolymer, making it easy to degrade and reducing environmental pollution. In addition, this application also adds polyborosiloxane, which, under the synergistic effect of the proportions of various components, greatly reduces the compression deformation and weight of the composite foam material, greatly improving the resilience of the composite foam material. The composite foam material is soft and comfortable, with excellent cushioning and rebound properties, and excellent wear resistance (far exceeding ordinary EVA foam materials), thereby meeting the performance requirements of sports shoe soles and providing consumers with a lasting comfortable experience.

[0040] The present application improves the properties of ethylene vinyl acetate copolymer by physically mixing polycaprolactone thermoplastic polyurethane elastomer with ethylene vinyl acetate copolymer, making it easy to degrade and reducing environmental pollution; at the same time, under the specific ratio of raw materials, the physical mixture is melt-blended with styrene-isoprene-butadiene copolymer hydrogenated polymer, thermoplastic vulcanizate and EPDM rubber to achieve a cross-linking reaction, thereby modifying the polycaprolactone, improving the strength and toughness, and lowering the melting point of the polycaprolactone thermoplastic polyurethane elastomer, so that it can be completely melt-blended with the ethylene vinyl acetate copolymer.

[0041] The present application improves the properties of ethylene vinyl acetate copolymer by physically mixing polycaprolactone thermoplastic polyurethane elastomer with ethylene vinyl acetate copolymer, making it easy to degrade and reducing environmental pollution; at the same time, under the specific ratio of raw materials, the physical mixture is melt-blended with styrene-isoprene-butadiene copolymer hydrogenated polymer, thermoplastic vulcanizate and EPDM rubber to achieve a cross-linking reaction, thereby modifying the polycaprolactone, improving the strength and toughness, and lowering the melting point of the polycaprolactone thermoplastic polyurethane elastomer, so that it can be completely melt-blended with the ethylene vinyl acetate copolymer.

[0042] The present application utilizes a highly elastic and compression-resistant composite foam material to be foamed, heated, shaped, and cooled to form a highly elastic and compression-resistant sole, thereby reducing the weight of a single sole by about 60%. At the same time, the density of a single sole is only about 40% of the density of a traditional sole. In addition, the sole is soft and comfortable, has excellent cushioning and rebound properties, is excellent in wear resistance (far exceeding ordinary EVA foam soles), and has good recovery performance, effectively solving the technical problem of the sole "becoming hard from soft and undergoing large permanent deformation" after long-term wear, greatly extending the service life of the sole, enhancing the durability of the sole, and improving the wearer's wearing experience.

[0043] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.

[0044] Undoubtedly, these and other objects of the present application will become more apparent after the following detailed description of the preferred embodiment with reference to various figures and drawings.

[0045] In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, one or several preferred embodiments are given below and described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] The accompanying drawings are used to provide further understanding of the present application and constitute a part of the specification. They are used together with the implementation methods of the present application to explain the present application and do not constitute a limitation to the present application.

[0047] In order to more clearly illustrate the implementation methods of the present application or the technical solutions in the prior art, a brief introduction will be given below to the drawings required for use in the implementation methods or the description of the prior art. Obviously, the drawings described below are only one or several implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on such drawings without any creative work.

[0048] Figure 1 This is a flow chart for preparing highly elastic and compression-resistant composite foam materials according to some embodiments of the present application;

[0049] Figure 2 This is a flow chart for preparing the highly elastic and compression-resistant composite foam material according to Example 1 of the present application;

[0050] Figure 3 This is a flow chart for preparing the highly elastic and compression-resistant composite foam material according to Example 2 of the present application;

[0051] Figure 4 This is a flow chart for preparing the highly elastic and compression-resistant composite foam material of Example 3 of the present application. DETAILED DESCRIPTION

[0052] The following will describe in detail the implementation methods of this application in conjunction with the accompanying drawings and examples, so that the application can fully understand how technical means are used to solve technical problems and achieve technical effects, and implement them accordingly. It should be noted that as long as there is no conflict, the various embodiments and the various features in each embodiment of this application can be combined with each other, and the resulting technical solutions are all within the scope of protection of this application.

[0053] While many specific details are set forth in the following description for purposes of explanation, in order to provide a thorough understanding of the embodiments of the present application, it will be apparent to those skilled in the art that the present application may be implemented without the specific details herein or the specific manner described.

[0054] According to some embodiments of the present application, a highly elastic and compression-resistant composite foam material is provided. The composite foam material comprises ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide.

[0055] Based on the total mass of the composite foam material,

[0056] The mass content of the ethylene vinyl acetate copolymer is 20.5%-33.5%, the mass content of the aliphatic thermoplastic polyurethane composite elastomer is 55%-60%, the mass content of the polyborosiloxane is 5%-10%, the mass content of the foaming agent is 2.5%-4%, the mass content of the active agent is 1%-2%, the mass content of the bridging agent is 0.7%-1.2%, the mass content of the coupling agent is 1.3%-1.8%, and the mass content of the zinc oxide is 1%-1.5%.

[0057] Ethylene-vinylacetate copolymer (EVA) has a vinyl acetate content of 5% to 40%. Compared to polyethylene, EVA incorporates vinyl acetate monomer into its molecular chain, reducing its crystallinity while improving its flexibility, impact resistance, filler compatibility, and heat-sealing properties. It is widely used in foamed shoe materials, functional greenhouse films, packaging films, hot-melt adhesives, wire and cable, and toys. In the field of foamed shoe materials, the vinyl acetate content is generally between 15% and 22%. Due to the softness, elasticity, and chemical resistance of EVA resin-blended foam products, they are widely used in the soles and interiors of mid- to high-end travel shoes, hiking boots, slippers, and sandals.

[0058] Polyborosiloxane is formed by reacting polydimethylsiloxane with boric acid at 250-300°C. In polyborosiloxane, electron-deficient boron atoms gain electrons from electron-paired oxygen atoms in adjacent molecules, forming BO crosslinks. These crosslinks absorb thermal energy and break at room temperature, resulting in composite foam materials exhibiting deformation properties similar to those of Silly Putty when subjected to stress. However, when subjected to high-speed impact, the molecular structure forms a network, exhibiting shock absorption and high resilience, as the impact time is shorter than the thermal rupture time of the crosslinks.

[0059] Foaming agent, which can make the object material into pores, can be divided into Chemical foaming agents and physical foaming agents and surface surfactants Chemical foaming agents are capable of releasing gases such as carbon dioxide and nitrogen after being decomposed by heating. polymerization thing Physical foaming agents are compounds that form pores in the composition of foam. These compounds are formed through a change in the physical form of a substance, such as the expansion of compressed gas, the volatilization of liquid, or the dissolution of solid. Foaming agents are highly surface active, effectively reducing the surface tension of liquids. They then form bubbles by arranging a double electron layer on the surface of the liquid film, enveloping air and forming bubbles. These bubbles then form the foam.

[0060] According to some embodiments of the present application, optionally, the foaming agent is one or a combination of two or more of azodicarbonamide, expandable ball polymer, and OBSH foaming agent.

[0061] Active agent, can increase the organic accelerator active , so that it can be fully utilized efficacy , thereby reducing Accelerator Dosage or shortening vulcanization The substance of time.

[0062] According to some embodiments of the present application, the active agent is optionally one or a combination of stearic acid and zinc stearate. Stearic acid plays an important role in the synthesis and processing of rubber: it is a widely used vulcanization activator in natural and synthetic rubber and latex, and can also be used as a plasticizer and softener. Stearic acid can be added as an emulsifier in the production of synthetic rubber, as a foaming agent in the manufacture of foam rubber, and as a release agent for rubber products.

[0063] Bridging agent, the scientific name of bridging agent is blocked water-based curing agent (non-ionic crosslinking agent), also known as bridging agent, curing agent, crosslinking agent, color fixing agent, adhesive, promoter, reinforcing agent, fastness enhancer. Its main component is blocked polyisocyanate. This series of curing agents can be used with Water-based resin ( Waterborne polyurethane , water-based acrylate, fluorine emulsion, Silicone emulsion etc.) to coexist stably for a long time, and the curing agent releases Isocyanates The (-NCO) group reacts with hydroxyl, carboxyl, amino and other groups on the water-based resin molecular chain to form a cross-linked structure, which can significantly improve the performance of the water-based resin.

[0064] According to some embodiments of the present application, optionally, the bridging agent is dicumyl peroxide (DCP).

[0065] Coupling agent is a kind of coupling agent with two different properties functional groupsThe biggest feature of the molecular structure of the substance is that it contains two groups with different chemical properties. One is an inorganic group that is easy to react with the surface of inorganic substances; the other is an organic group that can react with synthetic resin Or other polymers to undergo chemical reactions or generate hydrogen bonds and dissolve in them. Therefore, coupling agents are called "molecular bridges" to improve the interface between inorganic and organic substances, thereby greatly improving the performance of composite materials, such as physical properties, electrical properties, thermal properties, optical properties, etc. Coupling agents are used in the field of soles to improve the wear resistance and aging resistance of soles, and can reduce the amount of NR, thereby reducing costs. The role of coupling agents in composite materials is that they can react with certain groups on the surface of the reinforcing material, and with matrix The resin reacts to form an interface layer between the reinforcing material and the resin matrix. The interface layer can transfer stress, thereby enhancing the bonding strength between the reinforcing material and the resin, improving the performance of the composite material, and also preventing other media from penetrating into the interface, improving interface state, which is beneficial to the product's aging resistance, stress resistance and electrical insulation performance.

[0066] Zinc oxide is an inorganic substance with the chemical formula ZnO. zinc A kind of oxides . Hardly soluble in water, soluble in acid and strong base Zinc oxide is a commonly used chemical additive, widely used in plastics, silicate products, synthetic rubber 、 lubricating Oil , paints and coatings, ointments, adhesives, food, batteries, flame retardants And other products are in production.

[0067] This application is mainly based on aliphatic thermoplastic polyurethane composite elastomer, supplemented by ethylene vinyl acetate copolymer, which reduces the use of ethylene vinyl acetate copolymer, greatly reduces dependence on petrochemical raw materials, is beneficial to environmental protection, and through the physical mixing of polycaprolactone thermoplastic polyurethane elastomer and ethylene vinyl acetate copolymer, improves the properties of ethylene vinyl acetate copolymer, making it easy to degrade and reducing environmental pollution. In addition, this application also adds polyborosiloxane, which, under the synergistic effect of the proportions of various components, greatly reduces the compression deformation and weight of the composite foam material, greatly improving the resilience of the composite foam material. The composite foam material is soft and comfortable, with excellent cushioning and rebound properties, and excellent wear resistance (far exceeding ordinary EVA foam materials), thereby meeting the performance requirements of sports shoe soles and providing consumers with a lasting comfortable experience.

[0068] According to some embodiments of the present application, optionally, the aliphatic thermoplastic polyurethane composite elastomer includes polycaprolactone thermoplastic polyurethane elastomer, styrene-isoprene-butadiene hydrogenated copolymer, ethylene vinyl acetate copolymer, thermoplastic vulcanizate, ethylene propylene diene monomer rubber;

[0069] Based on the total mass of the aliphatic thermoplastic polyurethane composite elastomer,

[0070] The mass content of the polycaprolactone thermoplastic polyurethane elastomer is 40%-45%, the mass content of the styrene-isoprene-butadiene hydrogenated copolymer is 15%-20%, the mass content of the ethylene vinyl acetate copolymer is 20%-38%, the mass content of the thermoplastic vulcanized rubber is 2%-5%, and the mass content of the EPDM rubber is 5%-10%.

[0071] Polycaprolactone thermoplastic polyurethane elastomer, which is made by blending polycaprolactone with thermoplastic polyurethane elastomer.

[0072] Polycaprolactone (PCL) is a high-molecular-weight organic polymer produced by the ring-opening polymerization of ε-caprolactone monomers in the presence of a metal anion complex catalyst. By controlling the polymerization conditions, different molecular weights can be achieved. It appears as a white solid powder, is non-toxic, insoluble in water, and readily soluble in a variety of polar organic solvents. PCL exhibits excellent biocompatibility, compatibility with organic polymers, and biodegradability, making it suitable for use as a cell growth support material. It is compatible with a variety of conventional plastics and can be completely degraded in 6-12 months under natural conditions.

[0073] Thermoplastic polyurethane elastomer, made of high melting point crystalline Hard segment ( polyamide ) and amorphous soft segment ( Polyester or Gather ether ), wherein the hard segment is PA-6, PA-66, PA-12, etc., and the soft segment is composed of polyether or polyester. lactam 、 dicarboxylic acids 、 Gather Ether polyols The properties of the elastomer depend on the hard segment type and the two Block Due to the presence of hard segment polyamide, polyamide thermoplastic elastomer has excellent toughness 、 Chemical resistance 、 wear-resistant sex By selecting and controlling the block type, its Mechanics , heat and ChemicalPerformance can vary over a wide range.

[0074] Styrene-isoprene-butadiene hydrogenated copolymers were successfully prepared using anionic polymerization. Styrene (St)-isoprene (Ip)-butadiene (Bd) terpolymers were characterized by nuclear magnetic resonance (NMR), gas chromatography, gel permeation chromatography (GPC), transmission electron microscopy (TEM), and dynamic mechanical analysis. The properties of the material were compared with those of general-purpose rubber. The results showed that when the St content was below 30%, the copolymer tended to be randomly distributed. When the St content was above 35%, styrene block structures were formed. With increasing St content, the content of pendant groups in the copolymer decreased. The conversion of St, Ip, and Bd in the terpolymer increased with the total conversion. At low St content, the copolymer had a homogeneous microstructure. With increasing St content, phase separation occurred, and the loss peak shifted to higher temperatures and slightly increased in width. The block copolymer's physical and mechanical properties were comparable to those of other rubber materials, with superior wet skid resistance and lower rolling resistance than general-purpose rubber, making it an ideal rubber material for tire treads.

[0075] Ethylene-vinylacetate copolymer (EVA) has a vinyl acetate content of 5% to 40%. Compared to polyethylene, EVA incorporates vinyl acetate monomer into its molecular chain, resulting in lower crystallinity and improved flexibility, impact resistance, filler compatibility, and heat sealing properties. It is widely used in foamed shoe materials, functional greenhouse films, packaging films, hot-melt adhesives, wire and cable, and toys. In the field of foamed shoe materials, the vinyl acetate content is generally between 15% and 22%. Due to the softness, elasticity, and chemical resistance of EVA resin-blended foam products, they are widely used in the soles and interior materials of mid- to high-end travel shoes, hiking shoes, slippers, and sandals.

[0076] Thermoplastic vulcanizate (TPV) is mainly composed of two parts: plastic as the continuous phase and rubber as the dispersed phase. There are three common methods for preparing TPV, namely melt blending, solution blending, and latex blending. Melt blending is the most common method, and there are two main types of equipment used: mixer or Twin-screw extruder. Depending on the process, one device can be used alone, or both can be used. In industry, because the twin-screw extruder can be produced continuously, considering the stable quality, the twin-screw extruder has become the most common dynamic vulcanization equipment. The specific steps of dynamic vulcanization are as follows: First, the rubber and plastic are melted and blended in an internal mixer. When they are fully mixed, the vulcanizing agent is added. At this time, vulcanization is carried out while mixing. The faster the vulcanization speed, the more intense the mixing must be to ensure that the blend has good processing properties. Because granular rubber is sold, it is not necessary to use an internal mixer to mix plastic and rubber. A twin-screw extruder can be used directly for mixing. In the specific process, dynamic vulcanization can be divided into two steps. The plastic can be added to the rubber in two times to protect the plastic from the oxidation of the vulcanizer during dynamic vulcanization.

[0077] EPDM is a terpolymer of ethylene, propylene and non-conjugated dienes. Among them, the dienes have a special structure, and only one of the two bonds can be copolymerized. The unsaturated double bond is mainly used as a cross-linking point; the other unsaturated double bond will not become the main chain of the polymer, but only a side chain. The main polymer chain of EPDM is completely saturated, which makes Triple B C It is resistant to heat, light, oxygen, and especially ozone. EPDM is inherently non-polar, resistant to polar solutions and chemicals, has low water absorption, and exhibits good insulating properties. During the EPDM production process, its properties can be adjusted by varying the amount of the three monomers, the ethylene-propylene ratio, the molecular weight and its distribution, and the vulcanization method.

[0078] The present application improves the properties of ethylene vinyl acetate copolymer by physically mixing polycaprolactone thermoplastic polyurethane elastomer with ethylene vinyl acetate copolymer, making it easy to degrade and reducing environmental pollution; at the same time, under the specific ratio of raw materials, the physical mixture is melt-blended with styrene-isoprene-butadiene copolymer hydrogenated polymer, thermoplastic vulcanizate and EPDM rubber to achieve a cross-linking reaction, thereby modifying the polycaprolactone, improving the strength and toughness, and lowering the melting point of the polycaprolactone thermoplastic polyurethane elastomer, so that it can be completely melt-blended with the ethylene vinyl acetate copolymer.

[0079] According to some embodiments of the present application, optionally, the polyborosiloxane is formed by reacting polydimethylsiloxane and boric acid at 250° C.-300° C.

[0080] Polydimethylsiloxane is the chemical state of dimethyl silicone oil. Relative molecular massThe appearance ranges from colorless and transparent volatile liquid to extremely high viscosity liquid or silica gel. It is odorless and highly transparent. It has heat resistance, cold resistance, small viscosity change with temperature, water resistance, small surface tension, thermal conductivity, thermal conductivity coefficient of 0.134-0.159W / (m·K), light transmittance of 100%, polydimethylsiloxane is non-toxic and odorless, physiologically inert, and has good chemical stability. It has good electrical insulation, weather resistance, hydrophobicity, and high shear resistance, and can be used for a long time at -50℃~200℃. It has excellent physical properties and can be directly used for moisture-proof insulation, damping, shock absorption, defoaming, lubrication, polishing, etc. It is widely used as insulating lubrication, shockproof, oil and dustproof, dielectric fluid and heat carrier. And used as Defoaming 、 release agent , paints and daily chemical additives.

[0081] Boric acid is an inorganic compound with the chemical formula H3BO3. It is a white crystalline powder with a smooth feel and no odor.

[0082] Polysiloxane is an electron-deficient boron atom that obtains electrons from the electron-carrying oxygen atom in the adjacent molecule, thereby forming a BO cross-linking bond. The BO cross-linking bond will absorb heat energy and activate and break at room temperature. Therefore, when subjected to force, the composite foam material will have deformation characteristics like plasticine. When encountering high-speed impact, because the action time is shorter than the thermal break time of the cross-linking bond, it can instead allow the molecules to form a network structure, exhibiting characteristics such as shock absorption and high rebound.

[0083] Optionally, the reaction temperature of polydimethylsiloxane and boric acid is 250°C, 255°C, 260°C, 265°C, 270°C, 275°C, 280°C, 285°C, 290°C, 295°C, 300°C, or a value within the range obtained by combining any two of the above values.

[0084] According to some embodiments of the present application, optionally, the mass ratio of the polydimethylsiloxane to the boric acid is 25:2-4. By rationally controlling the mass ratio of polydimethylsiloxane to boric acid, the present application can ensure that the electron-deficient boron atoms obtain sufficient electrons from the electron-paired oxygen atoms in adjacent molecules, thereby forming a sufficient number of BO cross-links, so that the composite foam material can have the characteristics of compression deformation when subjected to force, and can form a sufficient network structure between molecules when subjected to high-speed impact, thereby exhibiting characteristics such as shock absorption and high rebound.

[0085] Optionally, the mass ratio of the polydimethylsiloxane to the boric acid is 25:2, 25:2.1, 25:2.2, 25:2.3, 25:2.4, 25:2.5, 25:2.6, 25:2.7, 25:2.8, 25:2.9, 25:3.0, 25:3.1, 25:3.2, 25:3.3, 25:3.4, 25:3.5, 25:3.6, 25:3.7, 25:3.8, 25:3.9, 25:4, or its value is within the range obtained by combining any two of the above values.

[0086] According to some embodiments of the present application, the reaction time is optionally 70 h to 74 h. By rationally controlling the reaction time of polydimethylsiloxane and boric acid, the present application can ensure that the electron-deficient boron atoms obtain sufficient electrons from the electron-paired oxygen atoms in the adjacent molecules, thereby forming a sufficient number of BO cross-links, so that the polyiodosiloxane can play a greater role.

[0087] Optionally, the reaction time of the polydimethylsiloxane and the boric acid is 70 h, 70.5 h, 71 h, 71.5 h, 72 h, 72.5 h, 73 h, 73.5 h, 74 h, or a value within the range obtained by combining any two of the above values.

[0088] According to some embodiments of the present application, the ethylene-vinyl acetate copolymer optionally has an acetic acid content of 28%. By selecting an ethylene-vinyl acetate copolymer having an acetic acid content of 28% for physical blending with a polycaprolactone thermoplastic polyurethane elastomer, the present application improves the properties of the ethylene-vinyl acetate copolymer, making it easier to degrade and reducing environmental pollution. Furthermore, the present application selects an ethylene-vinyl acetate copolymer having an acetic acid content of 28%, significantly improving the strength and toughness of the aliphatic thermoplastic polyurethane composite elastomer and lowering the melting point of the polycaprolactone thermoplastic polyurethane elastomer, enabling it to be completely melt-blended with the ethylene-vinyl acetate copolymer.

[0089] According to some embodiments of the present application, optionally, the ethylene-vinyl acetate copolymer includes an ethylene-vinyl acetate copolymer with an acetic acid content of 33% and an ethylene-vinyl acetate copolymer with an acetic acid content of 28%, wherein the weight ratio of the ethylene-vinyl acetate copolymer with an acetic acid content of 33% to the ethylene-vinyl acetate copolymer with an acetic acid content of 28% is 1:5-1:3. The present application, by reasonably selecting the weight ratio between the ethylene-vinyl acetate copolymer with an acetic acid content of 33% and the ethylene-vinyl acetate copolymer with an acetic acid content of 28%, and under the synergistic effect of the proportions of various components, greatly reduces the compression deformation and weight of the composite foam material, thereby greatly improving the resilience of the composite foam material. The composite foam material is soft and comfortable, has excellent cushioning and rebound properties, and is excellent in wear resistance (far exceeding that of ordinary EVA foam materials), thereby meeting the performance requirements of sports shoe soles and providing consumers with a lasting comfortable experience.

[0090] Optionally, the weight ratio of ethylene vinyl acetate copolymer with an acetic acid content of 33% to ethylene vinyl acetate copolymer with an acetic acid content of 28% is 1:5, 1:4.9, 1:4.8, 1:4.7, 1:4.6, 1:4.5, 1:4.4, 1:4.3, 1:4.2, 1:4.1, 1:4, 1:3.9, 1:3.8, 1:3.7, 1:3.6, 1:3.5, 1:3.4, 1:3.3, 1:3.2, 1:3.1, 1:3, or its value is within the range obtained by combining any two of the above values.

[0091] Reference Figure 1 , Figure 1 This is a flow chart for preparing highly elastic and compression-resistant composite foam materials according to some embodiments of the present application.

[0092] According to some embodiments of the present application, a method for preparing a highly elastic and compression-resistant composite foam material is provided. The preparation method comprises the following steps:

[0093] In a primary mixing step, ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, active agent, bridging agent, and zinc oxide are placed at 120° C. to 150° C. and kneaded for 7 min to 10 min to form a first mixed material;

[0094] Secondary mixing: adding the foaming agent and coupling agent to the first mixture, and mixing at 130-140°C for 2-3 minutes to form a second mixture;

[0095] Granulation: placing the second mixed material at 80° C.-90° C. for granulation to form a composite material;

[0096] Foaming: placing the composite material at 160°C-170°C for foaming to form a highly elastic and compression-resistant composite foam material.

[0097] The present invention first blends ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, an active agent, a bridging agent, and zinc oxide and performs a primary banburying process. A blowing agent and a coupling agent are then added and blended, followed by a secondary banburying process. The mixture is then granulated and foamed to produce a highly elastic and compression-resistant composite foam material. The composite foam material is soft and comfortable, has excellent cushioning and rebound properties, is highly wear-resistant (far exceeding ordinary EVA foam materials), and exhibits good recovery properties, thereby meeting the performance requirements of sports shoe soles and providing consumers with a long-lasting, comfortable experience.

[0098] Optionally, the temperature of the primary mixing is 120°C, 121°C, 122°C, 123°C, 124°C, 125°C, 126°C, 127°C, 128°C, 129°C, 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C, or 150°C, or its value is within the range obtained by combining any two of the above values.

[0099] Optionally, the mixing time is 7min, 7.1min, 7.2min, 7.3min, 7.4min, 7.5min, 7.6min, 7.7min, 7.8min, 7.9min, 8min, 8.1min, 8.2min, 8.3min, 8.4min, 8.5min, 8.6min, 8.7min, 8.8min, 8.9min, 9.1min, 9.2min, 9.3min, 9.4min, 9.5min, 9.6min, 9.7min, 9.8min, 9.9min, or 10min, or its value is within the range obtained by combining any two of the above values.

[0100] Optionally, the temperature of the secondary mixing is 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, or 140°C, or its value is within the range obtained by combining any two of the above values.

[0101] Optionally, the secondary mixing time is 2 min, 2.1 min, 2.2 min, 2.3 min, 2.4 min, 2.5 min, 2.6 min, 2.7 min, 2.8 min, 2.9 min, 3 min, or a value within the range obtained by combining any two of the above values.

[0102] Optionally, the granulation temperature is 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, or a value within the range obtained by combining any two of the above values.

[0103] Optionally, the foaming temperature is 160°C, 161°C, 162°C, 163°C, 164°C, 165°C, 166°C, 167°C, 168°C, 169°C, 170°C, or its value is within the range obtained by combining any two of the above values.

[0104] According to some embodiments of the present application, optionally, the preparation method further comprises a step of preparing an aliphatic thermoplastic polyurethane composite elastomer, and the preparation step is:

[0105] Adding polycaprolactone thermoplastic polyurethane elastomer, styrene-isoprene-butadiene copolymer hydrogenated polymer, ethylene vinyl acetate copolymer, thermoplastic vulcanized rubber, and ethylene propylene diene monomer rubber into a twin-screw extruder, blending and extruding to obtain an aliphatic thermoplastic polyurethane composite elastomer;

[0106] The blending time is 3 min to 5 min, and the blending temperature is 150° C. to 180° C.

[0107] The present application improves the properties of ethylene vinyl acetate copolymer by physically mixing polycaprolactone thermoplastic polyurethane elastomer with ethylene vinyl acetate copolymer, making it easy to degrade and reducing environmental pollution; at the same time, under the specific ratio of raw materials, the physical mixture is melt-blended with styrene-isoprene-butadiene copolymer hydrogenated polymer, thermoplastic vulcanizate and EPDM rubber to achieve a cross-linking reaction, thereby modifying the polycaprolactone, improving the strength and toughness, and lowering the melting point of the polycaprolactone thermoplastic polyurethane elastomer, so that it can be completely melt-blended with the ethylene vinyl acetate copolymer.

[0108] Optionally, the blending time is 3 min, 3.1 min, 3.2 min, 3.3 min, 3.4 min, 3.5 min, 3.6 min, 3.7 min, 3.8 min, 3.9 min, 4.0 min, 4.1 min, 4.2 min, 4.3 min, 4.4 min, 4.5 min, 4.6 min, 4.7 min, 4.8 min, 4.9 min, 5 min, or its value is within the range obtained by combining any two of the above values.

[0109] Optionally, the blending temperature is 150°C, 151°C, 152°C, 153°C, 154°C, 155°C, 156°C, 157°C, 158°C, 159°C, 160°C, 161°C, 162°C, 163°C, 164°C, 165°C, 166°C, 167°C, 168°C, 169°C, 170°C, 171°C, 172°C, 173°C, 174°C, 175°C, 176°C, 177°C, 178°C, 179°C, 180°C, or a value within the range obtained by combining any two of the above values.

[0110] According to some embodiments of the present application, optionally, the temperature of the twin-screw feeding zone of the twin-screw extruder is 100°C-120°C, and the temperature of the plasticizing zone is 130°C-150°C.

[0111] Optionally, the temperature in the twin-screw feeding zone is 100°C, 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C, 120°C, or a value within the range obtained by combining any two of the above values.

[0112] Optionally, the temperature in the plasticizing zone is 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C, 150°C, or a value within the range obtained by combining any two of the above values.

[0113] According to some embodiments of the present application, optionally, the twin-screw head temperature of the twin-screw extruder is 90°C-110°C.

[0114] Optionally, the twin-screw head temperature is 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, or its value is within the range obtained by combining any two of the above values.

[0115] According to some embodiments of the present application, optionally, the twin-screw speed of the twin-screw extruder is 20 rev / s-40 rev / s.

[0116] Optionally, the twin-screw speed is 20 rpm / S, 21 rpm / S, 22 rpm / S, 23 rpm / S, 24 rpm / S, 25 rpm / S, 26 rpm / S, 27 rpm / S, 28 rpm / S, 29 rpm / S, 30 rpm / S, 31 rpm / S, 32 rpm / S, 33 rpm / S, 34 rpm / S, 35 rpm / S, 36 rpm / S, 37 rpm / S, 38 rpm / S, 39 rpm, or 40 rpm, or its value is within the range obtained by combining any two of the above values.

[0117] According to some embodiments of the present application, a sole is provided. The sole is made of a highly elastic and compression-resistant composite foam material that is foamed using a foaming mold, and then heated, shaped, and cooled using a forming mold. The highly elastic and compression-resistant composite foam material includes ethylene-vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide.

[0118] Based on the total mass of the composite foam material,

[0119] The mass content of the ethylene vinyl acetate copolymer is 20.5%-33.5%, the mass content of the aliphatic thermoplastic polyurethane composite elastomer is 55%-60%, the mass content of the polyborosiloxane is 5%-10%, the mass content of the foaming agent is 2.5%-4%, the mass content of the active agent is 1%-2%, the mass content of the bridging agent is 0.7%-1.2%, the mass content of the coupling agent is 1.3%-1.8%, and the mass content of the zinc oxide is 1%-1.5%.

[0120] The present application utilizes a highly elastic and compression-resistant composite foam material to be foamed, heated, shaped, and cooled to form a highly elastic and compression-resistant sole, thereby reducing the weight of a single sole by about 60%. At the same time, the density of a single sole is only about 40% of the density of a traditional sole. In addition, the sole is soft and comfortable, has excellent cushioning and rebound properties, is excellent in wear resistance (far exceeding ordinary EVA foam soles), and has good recovery performance, effectively solving the technical problem of the sole "becoming hard from soft and undergoing large permanent deformation" after long-term wear, greatly extending the service life of the sole, enhancing the durability of the sole, and improving the wearer's wearing experience.

[0121] According to some embodiments of the present application, optionally, the foaming temperature is 160-180°C and the foaming time is 400-600 seconds. The present application significantly improves the foaming ratio by reasonably controlling the foaming temperature and foaming time of the highly elastic and compression-resistant composite foam material in the foaming mold.

[0122] Optionally, the foaming temperature is 160°C, 161°C, 162°C, 163°C, 164°C, 165°C, 167°C, 168°C, 169°C, 170°C, 171°C, 172°C, 173°C, 174°C, 175°C, 176°C, 178°C, 179°C, 180°C, or its value is within the range obtained by combining any two of the above values.

[0123] Optionally, the foaming time is 400s, 410s, 420s, 430s, 440s, 450s, 460s, 470s, 480s, 490s, 500s, 510s, 520s, 530s, 540s, 550s, 560s, 570s, 580s, 590s, or 600s, or its value is within the range obtained by combining any two of the above values.

[0124] According to some embodiments of the present application, optionally, the heating temperature is 165°C-185°C, the heating time is 500s-700s, and the shaping pressure is 80kg / m 2 -100kg / m 2 The present invention improves the structural stability of the sole by reasonably controlling parameters such as heating and shaping.

[0125] Optionally, the heating temperature is 165°C, 166°C, 167°C, 168°C, 169°C, 170°C, 171°C, 172°C, 173°C, 174°C, 175°C, 176°C, 177°C, 178°C, 179°C, 180°C, 181°C, 182°C, 183°C, 184°C, 185°C, or its value is within the range obtained by combining any two of the above values.

[0126] Optionally, the heating time is 500s, 510s, 520s, 530s, 540s, 550s, 560s, 570s, 580s, 590s, 600s, 610s, 620s, 630s, 640s, 650s, 670s, 680s, 690s, or 700s, or its value is within the range obtained by combining any two of the above values.

[0127] Optionally, the forming pressure is 80kg / m 2 、81kg / m 2 , 82kg / m 2 、83kg / m 2 、84kg / m 2 、85kg / m 2 、86kg / m 2 、87kg / m 2 ,88kg / m 2 、89kg / m 2, 90kg / m 2 , 91kg / m 2 , 92kg / m 2 , 93kg / m 2 , 94kg / m 2 , 95kg / m 2 , 96kg / m 2 , 97kg / m 2 , 98kg / m 2 , 99kg / m 2 , 100kg / m 2 , or its value is within the range obtained by combining any two of the above values.

[0128] Example 1

[0129] Reference Figure 2 , Figure 2 This is a flow chart for preparing the highly elastic and compression-resistant composite foam material of Example 1 of the present application.

[0130] This embodiment provides a highly elastic and compression-resistant composite foam material. The composite foam material includes an ethylene-vinyl acetate copolymer, an aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide. Based on the total mass of the composite foam material, the mass content of the ethylene-vinyl acetate copolymer is 33.5%, the mass content of the aliphatic thermoplastic polyurethane composite elastomer is 55%, the mass content of the polyborosiloxane is 5%, the mass content of the foaming agent is 2.5%, the mass content of the active agent is 1%, the mass content of the bridging agent is 0.7%, the mass content of the coupling agent is 1.3%, and the mass content of the zinc oxide is 1%.

[0131] The aliphatic thermoplastic polyurethane composite elastomer includes a polycaprolactone thermoplastic polyurethane elastomer, a styrene-isoprene-butadiene hydrogenated copolymer, an ethylene vinyl acetate copolymer (with an acetic acid content of 28%), a thermoplastic vulcanized rubber, and an EPDM rubber. Based on the total mass of the aliphatic thermoplastic polyurethane composite elastomer, the mass content of the polycaprolactone thermoplastic polyurethane elastomer is 40%, the mass content of the styrene-isoprene-butadiene hydrogenated copolymer is 15%, the mass content of the ethylene vinyl acetate copolymer (with an acetic acid content of 28%) is 38%, the mass content of the thermoplastic vulcanized rubber is 2%, and the mass content of the EPDM rubber is 5%.

[0132] The polyborosiloxane is prepared by reacting polydimethylsiloxane and boric acid (the mass ratio of the two is 25:2) at 250° C. for 74 hours.

[0133] This embodiment also provides a method for preparing a highly elastic and compression-resistant composite foam material. The preparation method comprises the following steps:

[0134] Preparation of an aliphatic thermoplastic polyurethane composite elastomer: adding a polycaprolactone thermoplastic polyurethane elastomer, a styrene-isoprene-butadiene hydrogenated copolymer, an ethylene vinyl acetate copolymer, a thermoplastic vulcanized rubber, and an EPDM rubber into a twin-screw extruder (the temperature of the twin-screw feeding zone of the twin-screw extruder is 100° C., the temperature of the plasticizing zone is 130° C., the temperature of the twin-screw die is 90° C., and the twin-screw speed is 20 rpm), blending (blending time is 3 minutes, blending temperature is 180° C.), and extruding to obtain an aliphatic thermoplastic polyurethane composite elastomer;

[0135] In a primary mixing process, ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, active agent, bridging agent, and zinc oxide are placed at 120° C. and kneaded for 10 minutes to form a first mixed material;

[0136] Secondary mixing: adding the foaming agent and coupling agent to the first mixture, and mixing at 130°C for 2 minutes to form a second mixture;

[0137] Granulation: placing the second mixed material at 80° C. for granulation to form a composite material;

[0138] Foaming: placing the composite material at 160° C. for foaming to form a highly elastic and compression-resistant composite foam material.

[0139] In addition, this embodiment provides a sole. The sole is made of a highly elastic and compression-resistant composite foam material that is foamed by a foaming mold (foaming temperature is 160°C, foaming time is 600s), then heated by a forming mold (heating temperature is 165°C, heating time is 700s), and shaped (forming pressure is 80kg / m 2 ), cooled and made.

[0140] Example 2

[0141] Reference Figure 3 , Figure 3 This is a flow chart for preparing the highly elastic and compression-resistant composite foam material of Example 2 of the present application.

[0142] This embodiment provides a highly elastic and compression-resistant composite foam material. The composite foam material includes an ethylene-vinyl acetate copolymer, an aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide. Based on the total mass of the composite foam material, the mass content of the ethylene-vinyl acetate copolymer is 27%, the mass content of the aliphatic thermoplastic polyurethane composite elastomer is 57.5%, the mass content of the polyborosiloxane is 7.5%, the mass content of the foaming agent is 3.25%, the mass content of the active agent is 1.5%, the mass content of the bridging agent is 0.95%, the mass content of the coupling agent is 1.55%, and the mass content of the zinc oxide is 1.25%.

[0143] The aliphatic thermoplastic polyurethane composite elastomer includes a polycaprolactone thermoplastic polyurethane elastomer, a styrene-isoprene-butadiene hydrogenated copolymer, an ethylene vinyl acetate copolymer (with an acetic acid content of 28%), a thermoplastic vulcanized rubber, and an EPDM rubber. Based on the total mass of the aliphatic thermoplastic polyurethane composite elastomer, the mass content of the polycaprolactone thermoplastic polyurethane elastomer is 42.5%, the mass content of the styrene-isoprene-butadiene hydrogenated copolymer is 17.5%, the mass content of the ethylene vinyl acetate copolymer (with an acetic acid content of 28%) is 29%, the mass content of the thermoplastic vulcanized rubber is 3.5%, and the mass content of the EPDM rubber is 7.5%.

[0144] The polyborosiloxane is prepared by reacting polydimethylsiloxane and boric acid (the mass ratio of the two is 25:3) at 275° C. for 72 hours.

[0145] This embodiment also provides a method for preparing a highly elastic and compression-resistant composite foam material. The preparation method comprises the following steps:

[0146] Preparation of an aliphatic thermoplastic polyurethane composite elastomer: adding a polycaprolactone thermoplastic polyurethane elastomer, a styrene-isoprene-butadiene hydrogenated copolymer, an ethylene vinyl acetate copolymer, a thermoplastic vulcanizate, and an EPDM rubber into a twin-screw extruder (the temperature of the twin-screw feeding zone of the twin-screw extruder is 110° C., the temperature of the plasticizing zone is 140° C., the temperature of the twin-screw die is 100° C., and the twin-screw speed is 30 rpm), blending (blending time is 4 minutes, blending temperature is 165° C.), and extruding to obtain an aliphatic thermoplastic polyurethane composite elastomer;

[0147] In a primary mixing process, ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, active agent, bridging agent, and zinc oxide are placed at 135° C. and kneaded for 8.5 minutes to form a first mixed material;

[0148] Secondary mixing: adding the foaming agent and coupling agent to the first mixture, and mixing at 135°C for 2.5 minutes to form a second mixture;

[0149] Granulation: placing the second mixed material at 85° C. for granulation to form a composite material;

[0150] Foaming: placing the composite material at 165° C. for foaming to form a highly elastic and compression-resistant composite foam material.

[0151] In addition, this embodiment provides a sole. The sole is made of a highly elastic and compression-resistant composite foam material that is foamed by a foaming mold (foaming temperature is 170°C, foaming time is 500s), then heated by a forming mold (heating temperature is 170°C, heating time is 600s), and shaped (forming pressure is 90kg / m 2 ), cooled and made.

[0152] Example 3

[0153] Reference Figure 4 , Figure 4 This is a flow chart for preparing the highly elastic and compression-resistant composite foam material of Example 3 of the present application.

[0154] This embodiment provides a highly elastic and compression-resistant composite foam material. The composite foam material includes an ethylene-vinyl acetate copolymer, an aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide. Based on the total mass of the composite foam material, the mass content of the ethylene-vinyl acetate copolymer is 20.5%, the mass content of the aliphatic thermoplastic polyurethane composite elastomer is 60%, the mass content of the polyborosiloxane is 10%, the mass content of the foaming agent is 4%, the mass content of the active agent is 2%, the mass content of the bridging agent is 1.2%, the mass content of the coupling agent is 1.8%, and the mass content of the zinc oxide is 1.5%.

[0155] The aliphatic thermoplastic polyurethane composite elastomer includes a polycaprolactone thermoplastic polyurethane elastomer, a styrene-isoprene-butadiene hydrogenated copolymer, an ethylene vinyl acetate copolymer (with an acetic acid content of 28%), a thermoplastic vulcanized rubber, and an EPDM rubber. Based on the total mass of the aliphatic thermoplastic polyurethane composite elastomer, the mass content of the polycaprolactone thermoplastic polyurethane elastomer is 45%, the mass content of the styrene-isoprene-butadiene hydrogenated copolymer is 20%, the mass content of the ethylene vinyl acetate copolymer (with an acetic acid content of 28%) is 20%, the mass content of the thermoplastic vulcanized rubber is 5%, and the mass content of the EPDM rubber is 10%.

[0156] The polyborosiloxane is prepared by reacting polydimethylsiloxane and boric acid (the mass ratio of the two is 25:4) at 300° C. for 70 hours.

[0157] This embodiment also provides a method for preparing a highly elastic and compression-resistant composite foam material. The preparation method comprises the following steps:

[0158] Preparation of an aliphatic thermoplastic polyurethane composite elastomer: adding a polycaprolactone thermoplastic polyurethane elastomer, a styrene-isoprene-butadiene hydrogenated copolymer, an ethylene vinyl acetate copolymer, a thermoplastic vulcanizate, and an EPDM rubber into a twin-screw extruder (the temperature of the twin-screw feeding zone of the twin-screw extruder is 120° C., the temperature of the plasticizing zone is 150° C., the temperature of the twin-screw die is 110° C., and the twin-screw speed is 40 rpm), blending (blending time is 5 minutes, blending temperature is 150° C.), and extruding to obtain an aliphatic thermoplastic polyurethane composite elastomer;

[0159] In a primary mixing process, ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, active agent, bridging agent, and zinc oxide are placed at 150° C. and kneaded for 7 minutes to form a first mixed material;

[0160] Secondary mixing: adding the foaming agent and coupling agent to the first mixture, and mixing at 140°C for 2 minutes to form a second mixture;

[0161] Granulation: placing the second mixed material at 90° C. for granulation to form a composite material;

[0162] Foaming: placing the composite material at 170° C. for foaming to form a highly elastic and compression-resistant composite foam material.

[0163] In addition, this embodiment provides a sole. The sole is made of a highly elastic and compression-resistant composite foam material that is foamed by a foaming mold (foaming temperature is 180°C, foaming time is 400s), then heated by a forming mold (heating temperature is 185°C, heating time is 500s), and shaped (shaping pressure is 100kg / m 2 ), cooled and made.

[0164] Comparative Example 1

[0165] The difference between Comparative Example 1 and Example 1 is that no aliphatic thermoplastic polyurethane composite elastomer is added in Comparative Example 1.

[0166] Comparative Example 1 provides a composite foam material. The composite foam material includes ethylene vinyl acetate copolymer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide. Based on the total mass of the composite foam material, the mass content of the ethylene vinyl acetate copolymer is 88.5%, the mass content of the polyborosiloxane is 5%, the mass content of the foaming agent is 2.5%, the mass content of the active agent is 1%, the mass content of the bridging agent is 0.7%, the mass content of the coupling agent is 1.3%, and the mass content of the zinc oxide is 1%.

[0167] The polyborosiloxane is prepared by reacting polydimethylsiloxane and boric acid (the mass ratio of the two is 25:2) at 250° C. for 74 hours.

[0168] Comparative Example 1 also provides a method for preparing a composite foam material. The preparation method comprises the following steps:

[0169] In a first mixing step, ethylene vinyl acetate copolymer, polyborosiloxane, active agent, bridging agent and zinc oxide are placed at 120° C. and kneaded for 10 minutes to form a first mixed material;

[0170] Secondary mixing: adding the foaming agent and coupling agent to the first mixture, and mixing at 130°C for 2 minutes to form a second mixture;

[0171] Granulation: placing the second mixed material at 80° C. for granulation to form a composite material;

[0172] Foaming: placing the composite material at 160° C. for foaming to form a composite foam material.

[0173] In addition, Comparative Example 1 provides a sole. The sole is made of a composite foam material that is foamed by a foaming mold (foaming temperature is 160°C, foaming time is 600s), and then heated by a forming mold (heating temperature is 165°C, heating time is 700s), and shaped (forming pressure is 80kg / m 2 ), cooled and made.

[0174] Comparative Example 2

[0175] The difference between Comparative Example 2 and Example 2 is that no aliphatic thermoplastic polyurethane composite elastomer is added in Comparative Example 2.

[0176] Comparative Example 2 provides a composite foam material. The composite foam material includes ethylene vinyl acetate copolymer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide. Based on the total mass of the composite foam material, the mass content of the ethylene vinyl acetate copolymer is 84.5%, the mass content of the polyborosiloxane is 7.5%, the mass content of the foaming agent is 3.25%, the mass content of the active agent is 1.5%, the mass content of the bridging agent is 0.95%, the mass content of the coupling agent is 1.55%, and the mass content of the zinc oxide is 1.25%.

[0177] The polyborosiloxane is prepared by reacting polydimethylsiloxane and boric acid (the mass ratio of the two is 25:3) at 275° C. for 72 hours.

[0178] Comparative Example 2 also provides a method for preparing a composite foam material. The preparation method comprises the following steps:

[0179] In a first mixing step, ethylene vinyl acetate copolymer, polyborosiloxane, active agent, bridging agent, and zinc oxide are placed at 135° C. and kneaded for 8.5 minutes to form a first mixed material;

[0180] Secondary mixing: adding the foaming agent and coupling agent to the first mixture, and mixing at 135°C for 2.5 minutes to form a second mixture;

[0181] Granulation: placing the second mixed material at 85° C. for granulation to form a composite material;

[0182] Foaming: placing the composite material at 165° C. for foaming to form a composite foam material.

[0183] In addition, Comparative Example 2 provides a sole. The sole is made of a composite foam material that is foamed by a foaming mold (foaming temperature is 170°C, foaming time is 500s), then heated by a forming mold (heating temperature is 170°C, heating time is 600s), and shaped (forming pressure is 90kg / m 2 ), cooled and made.

[0184] Comparative Example 3

[0185] The difference between Comparative Example 3 and Example 3 is that no aliphatic thermoplastic polyurethane composite elastomer is added in Comparative Example 3.

[0186] Comparative Example 3 provides a composite foam material. The composite foam material includes ethylene vinyl acetate copolymer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide. Based on the total mass of the composite foam material, the mass content of the ethylene vinyl acetate copolymer is 80.5%, the mass content of the polyborosiloxane is 10%, the mass content of the foaming agent is 4%, the mass content of the active agent is 2%, the mass content of the bridging agent is 1.2%, the mass content of the coupling agent is 1.8%, and the mass content of the zinc oxide is 1.5%.

[0187] The polyborosiloxane is prepared by reacting polydimethylsiloxane and boric acid (the mass ratio of the two is 25:4) at 300° C. for 70 hours.

[0188] Comparative Example 3 also provides a method for preparing a composite foam material. The preparation method comprises the following steps:

[0189] In a primary mixing process, ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, active agent, bridging agent, and zinc oxide are placed at 150° C. and kneaded for 7 minutes to form a first mixed material;

[0190] Secondary mixing: adding the foaming agent and coupling agent to the first mixture, and mixing at 140°C for 2 minutes to form a second mixture;

[0191] Granulation: placing the second mixed material at 90° C. for granulation to form a composite material;

[0192] Foaming: placing the composite material at 170° C. for foaming to form a highly elastic and compression-resistant composite foam material.

[0193] In addition, Comparative Example 3 provides a sole. The sole is made of a composite foam material that is foamed by a foaming mold (foaming temperature is 180°C, foaming time is 400s), then heated by a forming mold (heating temperature is 185°C, heating time is 500s), shaped (forming pressure is 100kg / m 2 ), cooled and made.

[0194] Table 1 Physical property test results of composite foam materials obtained from Examples 1-3 and Comparative Examples 1-3

[0195]

[0196] Table 2 Physical property test results of the soles obtained in Examples 1-3 and Comparative Examples 1-4

[0197]

[0198]

[0199] As can be seen from Table 1-2, various properties (hardness, density, resilience, tensile strength, thermal shrinkage, compression set, elongation at break, and delamination and tearing) of Examples 1-3 are all superior to those of Comparative Examples 1-3. The soles of Examples 1-3 are soft and comfortable, have excellent cushioning and resilience properties, are excellent in wear resistance (far exceeding ordinary EVA foam soles), and have good recovery performance. They effectively solve the technical problem of "the sole becoming hard from soft and undergoing large permanent deformation" after long-term wear, greatly extend the service life of the sole, enhance the durability of the sole, and improve the wearer's wearing experience.

[0200] It should be understood that the embodiments disclosed herein are not limited to the specific processing steps or materials disclosed herein, but should be extended to equivalent substitutions of such features understood by those skilled in the relevant art. It should also be understood that the terminology used herein is for the purpose of describing specific embodiments only and is not intended to be limiting.

[0201] The "embodiment" mentioned in the specification means that a particular feature or characteristic described in conjunction with the embodiment is included in at least one embodiment of the present application. Therefore, the phrase or "embodiment" appearing in various places throughout the specification does not necessarily refer to the same embodiment.

[0202] Furthermore, the described features or characteristics may be incorporated into one or more embodiments in any other suitable manner. In the above description, some specific details, such as thickness, quantity, etc., are provided to provide a comprehensive understanding of the embodiments of the present application. However, those skilled in the relevant art will appreciate that the present application may be implemented without one or more of the above specific details or may also be implemented using other methods, components, materials, etc.

Claims

1. A highly elastic and compression-resistant composite foam material, characterized in that: The composite foaming material comprises ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent and zinc oxide; Based on the total mass of the composite foam material, The mass content of the ethylene vinyl acetate copolymer is 20.5%-33.5%, the mass content of the aliphatic thermoplastic polyurethane composite elastomer is 55%-60%, the mass content of the polyborosiloxane is 5%-10%, the mass content of the foaming agent is 2.5%-4%, the mass content of the active agent is 1%-2%, the mass content of the bridging agent is 0.7%-1.2%, the mass content of the coupling agent is 1.3%-1.8%, and the mass content of the zinc oxide is 1%-1.5%; The aliphatic thermoplastic polyurethane composite elastomer includes polycaprolactone thermoplastic polyurethane elastomer, styrene-isoprene-butadiene hydrogenated copolymer, ethylene vinyl acetate copolymer, thermoplastic vulcanized rubber, and EPDM rubber, wherein the polycaprolactone thermoplastic polyurethane elastomer is prepared by blending polycaprolactone with thermoplastic polyurethane elastomer. Based on the total mass of the aliphatic thermoplastic polyurethane composite elastomer, The mass content of the polycaprolactone thermoplastic polyurethane elastomer is 40%-45%, the mass content of the styrene-isoprene-butadiene hydrogenated copolymer is 15%-20%, the mass content of the ethylene vinyl acetate copolymer is 20%-38%, the mass content of the thermoplastic vulcanized rubber is 2%-5%, and the mass content of the EPDM rubber is 5%-10%.

2. The high-elasticity and compression-resistant composite foam material according to claim 1, characterized in that: The polyborosiloxane is prepared by reacting polydimethylsiloxane with boric acid at 250-300°C.

3. The high-elasticity and compression-resistant composite foam material according to claim 2, characterized in that: The mass ratio of the polydimethylsiloxane to the boric acid is 25:2-4.

4. The high-elasticity and compression-resistant composite foam material according to claim 2, characterized in that: The reaction time is 70h-74h.

5. The high-elasticity and compression-resistant composite foam material according to claim 1, characterized in that: The acetic acid content in the ethylene vinyl acetate copolymer is 28%.

6. The high-elasticity and compression-resistant composite foam material according to claim 1, characterized in that: The ethylene vinyl acetate copolymer comprises an ethylene vinyl acetate copolymer with an acetic acid content of 33% and an ethylene vinyl acetate copolymer with an acetic acid content of 28%, wherein the weight ratio of the ethylene vinyl acetate copolymer with an acetic acid content of 33% to the ethylene vinyl acetate copolymer with an acetic acid content of 28% is 1:5-1:

3.

7. A method for preparing a highly elastic and compression-resistant composite foam material according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: In a primary mixing step, ethylene vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, active agent, bridging agent, and zinc oxide are placed at 120° C. to 150° C. and kneaded for 7 min to 10 min to form a first mixed material; Secondary mixing: adding the foaming agent and coupling agent to the first mixture, and mixing at 130-140°C for 2-3 minutes to form a second mixture; Granulation: placing the second mixed material at 80° C.-90° C. for granulation to form a composite material; Foaming: placing the composite material at 160-170°C for foaming to form a highly elastic and compression-resistant composite foam material; The preparation steps of the aliphatic thermoplastic polyurethane composite elastomer are as follows: Adding polycaprolactone thermoplastic polyurethane elastomer, styrene-isoprene-butadiene copolymer hydrogenated polymer, ethylene vinyl acetate copolymer, thermoplastic vulcanized rubber, and ethylene propylene diene monomer rubber into a twin-screw extruder, blending and extruding to obtain an aliphatic thermoplastic polyurethane composite elastomer; The blending time is 3 min to 5 min, and the blending temperature is 150° C. to 180° C.

8. The method for preparing a high-elasticity and compression-resistant composite foam material according to claim 7, characterized in that: The temperature of the twin-screw feeding zone of the twin-screw extruder is 100℃-120℃, and the temperature of the plasticizing zone is 130℃-150℃.

9. The method for preparing a high-elasticity and compression-resistant composite foam material according to claim 7, characterized in that: The twin-screw head temperature of the twin-screw extruder is 90°C-110°C.

10. The method for preparing a highly elastic and compression-resistant composite foam material according to claim 7, characterized in that: The twin-screw speed of the twin-screw extruder is 20 rev / s-40 rev / s.

11. A shoe sole, characterized in that: The sole is made of a highly elastic and compression-resistant composite foam material that is foamed in a foaming mold and then heated, shaped, and cooled in a forming mold. The highly elastic and compression-resistant composite foam material includes ethylene-vinyl acetate copolymer, aliphatic thermoplastic polyurethane composite elastomer, polyborosiloxane, a foaming agent, an active agent, a bridging agent, a coupling agent, and zinc oxide. Based on the total mass of the composite foam material, The mass content of the ethylene vinyl acetate copolymer is 20.5%-33.5%, the mass content of the aliphatic thermoplastic polyurethane composite elastomer is 55%-60%, the mass content of the polyborosiloxane is 5%-10%, the mass content of the foaming agent is 2.5%-4%, the mass content of the active agent is 1%-2%, the mass content of the bridging agent is 0.7%-1.2%, the mass content of the coupling agent is 1.3%-1.8%, and the mass content of the zinc oxide is 1%-1.5%; The aliphatic thermoplastic polyurethane composite elastomer comprises polycaprolactone thermoplastic polyurethane elastomer, styrene-isoprene-butadiene hydrogenated copolymer, ethylene vinyl acetate copolymer, thermoplastic vulcanized rubber, and EPDM rubber, wherein the polycaprolactone thermoplastic polyurethane elastomer is prepared by blending polycaprolactone with thermoplastic polyurethane elastomer. Based on the total mass of the aliphatic thermoplastic polyurethane composite elastomer, The mass content of the polycaprolactone thermoplastic polyurethane elastomer is 40%-45%, the mass content of the styrene-isoprene-butadiene hydrogenated copolymer is 15%-20%, the mass content of the ethylene vinyl acetate copolymer is 20%-38%, the mass content of the thermoplastic vulcanized rubber is 2%-5%, and the mass content of the EPDM rubber is 5%-10%.

12. The sole according to claim 11, characterized in that The foaming temperature is 160°C-180°C, and the foaming time is 400s-600s.

13. The sole according to claim 11, characterized in that The heating temperature is 165℃-185℃, the heating time is 500s-700s, and the shaping pressure is 80kg / m 2 -100 kg / m 2 .

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