1. A super-elastic fatigue-resistant foaming material comprises the following components in parts by weight:

100 parts of thermoplastic elastomer resin, 0.5-50 parts of amorphous metal powder, 0.2-1 part of antioxidant, 0-1.5 parts of stearic acid and 0-1 part of foam stabilizer.

2. The superelastic fatigue-resistant foam material of claim 1, wherein said amorphous metal powder is selected from one or more of an iron-based alloy, a nickel-based alloy, an aluminum-based alloy, a zirconium-based alloy, a cobalt-based alloy, a copper-based alloy, a titanium-based alloy, a magnesium-based alloy, a calcium-based alloy, a platinum-based alloy, a palladium-based alloy, a gold-based alloy, a hafnium-based alloy, and a rare earth-based alloy powder.

3. The superelastic fatigue-resistant foam material according to claim 1, the thermoplastic elastomer resin is selected from one or more of thermoplastic polyurethane, nylon elastomer, thermoplastic polyester elastomer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-butylene-styrene block copolymer, styrene-ethylene/propylene-styrene block copolymer, ethylene-octene random copolymer, ethylene vinyl acetate, thermoplastic vulcanized elastomer, trans-1, 4-polyisoprene rubber, syndiotactic 1,2 polybutadiene, polyvinyl chloride, thermoplastic chlorinated polyethylene, polydimethylsiloxane and organic fluorine thermoplastic elastomer.

4. A method for preparing the superelastic fatigue-resistant foam material according to any one of claims 1-3, comprising the following steps:

a) premixing 100 parts of thermoplastic elastomer resin, 0.5-50 parts of amorphous metal powder, 0.2-1 part of antioxidant, 0-1.5 parts of stearic acid and 0-1 part of foam stabilizer, melting and mixing, extruding and granulating to obtain thermoplastic elastomer composite particles;

b) preheating the thermoplastic elastomer composite particles obtained in the step a), putting the thermoplastic elastomer composite particles into a mold, closing the mold, placing the mold in a closed container, introducing gas into the container, heating the container to ensure that the gas reaching a supercritical state soaks and saturates the thermoplastic elastomer composite particles, and finally quickly relieving the pressure and opening the mold to obtain the super-elastic fatigue-resistant foaming material;

or extruding the thermoplastic elastomer composite particles obtained in the step a) into a plate by a double screw or injecting the plate into a special-shaped part with a 3D structure; and (3) soaking the sheet or the special-shaped part in a high-pressure fluid atmosphere until the sheet or the special-shaped part is balanced, and then quickly relieving pressure to obtain the super-elastic fatigue-resistant foaming material.

5. The method according to claim 4, wherein the temperature of the melt-kneading in the step a) is 130 to 210 ℃ and the time is 1 to 10 min.

6. The method according to claim 4, wherein the screw temperature for the extruding or ejecting in the step b) is 100 to 200 ℃.

7. The preparation method according to claim 4, wherein the temperature for impregnation saturation in step b) is 80-90 ℃, the pressure is 5-50 MPa, and the time is 10-120 min.

8. The preparation method of claim 4, wherein the rapid pressure relief rate in the step b) is 5-30 MPa/s.

9. Use of the superelastic fatigue-resistant foam material according to any one of claims 1-3 or the superelastic fatigue-resistant foam material prepared by the preparation method according to any one of claims 4-8 in a midsole of a sports shoe sole, an automobile cushion or a shock pad for sports equipment.

Background

High elasticity foams have a wide range of applications, particularly in the sporting goods industry, such as the midsole material of sports shoes, which is the core technology of shoes, has the functions of reducing impact when falling to the ground, providing forward propulsion, safety protection and comfort, and is generally a foam material of a thermoplastic elastomer, mainly relating to ethylene vinyl acetate polymers, polyolefin elastomers, thermoplastic polyurethanes, thermoplastic elastomer polyesters, thermoplastic nylon elastomers, and the like. Thermoplastic elastomer materials tend to have better resilience properties after being expanded by foaming. Patent CN201610150971.3 discloses an ultralight high-elastic environment-friendly sole and a preparation method thereof, which uses thermoplastic elastomer materials such as EVA, polyolefin block copolymer (OBC) and the like as a main matrix, and carries out supercritical foaming after crosslinking to obtain a microcellular foamed midsole.

However, polymer materials are viscoelastic, and when they are deformed, they are not completely deformed elastically but are deformed plastically. When plastic deformation occurs, energy is consumed due to slippage between molecules or crystal planes, frictional heating and the like, so that the original energy cannot be completely stored as deformation energy and released in the recovery process. The part of energy lost is attributed to the energy loss, so that the elasticity of the thermoplastic elastomer material has a limit. The rebound rate of the current thermoplastic nylon elastomer foaming material can reach more than 65 percent and is higher than that of other elastomer shoe materials, and the density of the material is lower than 0.1g/cm³For example, patent CN201810534118.0 discloses an ionic/covalent crosslinking foaming high-elastic wear-resistant super-elastic material using polyether block amide as matrixThe light sports sole material and the preparation method thereof realize the ultra-light of the cross-linked foaming sole material by foaming through the chemical foaming agent, and simultaneously meet the requirements of high elasticity, buffering, shock absorption and wear resistance. But its fatigue resistance is not ideal.

To obtain ultra-high resilience, the polymer material has a limitation of energy regression rate due to heat generation caused by the slippage of the molecular chain. The inorganic material is mainly used as a filler to improve the wear resistance, deformation resistance, tearing resistance or tensile strength of the composite.

CN201710152004.5 provides a graphene/polymer light high-elastic soft composite foam material and a preparation method thereof. By introducing the graphene, the mechanical property of the composite material is effectively reinforced, so that the composite foam material is light in weight, wear-resistant, deformation-resistant and tear-resistant.

The patent with the application number of CN201811186084.7 discloses a high-elasticity wear-resistant foamed rubber and a preparation method thereof, wherein a plurality of high-elasticity rubbers are taken as main matrixes, and fiber reinforcing fillers are also used in a raw material formula, so that the elasticity and the tensile strength of the foamed rubber are further improved.

Disclosure of Invention

In view of the above, the present invention provides a superelastic fatigue-resistant material and a method for preparing the same, wherein the superelastic fatigue-resistant material has ultrahigh resilience characteristics and good compression resistance.

The invention provides a super-elastic fatigue-resistant foaming material which comprises the following components in parts by weight:

100 parts of thermoplastic elastomer resin, 0.5-50 parts of amorphous metal powder, 0.2-1 part of antioxidant, 0-1.5 parts of stearic acid and 0-1 part of foam stabilizer.

Preferably, the amorphous metal powder is selected from one or more of iron-based alloy, nickel-based alloy, aluminum-based alloy, zirconium-based alloy, cobalt-based alloy, copper-based alloy, titanium-based alloy, magnesium-based alloy, calcium-based alloy, platinum-based alloy, palladium-based alloy, gold-based alloy, hafnium-based alloy, and rare earth-based alloy powder.

Preferably, the thermoplastic elastomer resin is selected from one or more of thermoplastic polyurethane, nylon elastomer, thermoplastic polyester elastomer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-butylene-styrene block copolymer, styrene-ethylene/propylene-styrene block copolymer, ethylene-octene random copolymer, ethylene vinyl acetate, thermoplastic vulcanizate elastomer, trans-1, 4-polyisoprene rubber, syndiotactic 1,2 polybutadiene, polyvinyl chloride, thermoplastic chlorinated polyethylene, polydimethylsiloxane and organic fluorine type thermoplastic elastomer.

The invention provides a preparation method of the superelastic fatigue-resistant foam material in the technical scheme, which comprises the following steps:

a) premixing 100 parts of thermoplastic elastomer resin, 0.5-50 parts of amorphous metal powder, 0.2-1 part of antioxidant, 0-1.5 parts of stearic acid and 0-1 part of foam stabilizer, melting and mixing, extruding and granulating to obtain thermoplastic elastomer composite particles;

b) preheating the thermoplastic elastomer composite particles obtained in the step a), putting the thermoplastic elastomer composite particles into a mold, closing the mold, placing the mold in a closed container, introducing gas into the container, heating the container to ensure that the gas reaching a supercritical state soaks and saturates the thermoplastic elastomer composite particles, and finally quickly relieving the pressure and opening the mold to obtain the super-elastic fatigue-resistant foaming material;

or extruding the thermoplastic elastomer composite particles obtained in the step a) into a plate by a double screw or injecting the plate into a special-shaped part with a 3D structure; and (3) soaking the sheet or the special-shaped part in a high-pressure fluid atmosphere until the sheet or the special-shaped part is balanced, and then quickly relieving pressure to obtain the super-elastic fatigue-resistant foaming material.

Preferably, the temperature of the melt mixing in the step a) is 130-210 ℃, and the time is 1-10 min.

Preferably, the temperature of the screw for extruding or ejecting in the step b) is 100-200 ℃.

Preferably, the impregnation saturation temperature in the step b) is 80-90 ℃, the pressure is 5-50 MPa, and the time is 10-120 min.

Preferably, the pressure relief rate of the rapid pressure relief in the step b) is 5-30 MPa/s.

The invention provides an application of the superelastic fatigue-resistant foam material in the technical scheme or the superelastic fatigue-resistant foam material prepared by the preparation method in the technical scheme in a sports shoe sole midsole, an automobile cushion or a sports equipment shock pad.

The invention provides a super-elastic fatigue-resistant foaming material which comprises, by weight, 100 parts of thermoplastic elastomer resin, 0.5-50 parts of amorphous metal powder, 0.2-1 part of antioxidant, 0-1.5 parts of stearic acid and 0-1 part of foam stabilizer. Compared with the prior art, the super-elastic fatigue-resistant foaming material provided by the invention adopts specific materials and content components, so that better interaction is realized; the product has light density, super high resilience characteristic and excellent compression deformation resistance characteristic to when promoting sports shoes elasticity greatly, have lasting comfortable and lasting shock-absorbing function concurrently, give the person of dress good and the experience of running.

Drawings

FIG. 1 is a top view of a super-elastic fatigue-resistant foam provided in example 1 of the present invention;

FIG. 2 is a cell structure diagram of the materials prepared in example 1 and comparative example 1;

FIG. 3 is a photograph of a cross-section of a superelastic fatigue-resistant foam material according to example 2 of the present invention;

FIG. 4 is a photograph of a cross-section of a superelastic fatigue-resistant foam material according to example 3 of the present invention;

FIG. 5 is a photograph of a cross-section of a superelastic fatigue-resistant foam material according to example 4 of the present invention;

FIG. 6 is a photograph of a cross-section of a superelastic fatigue-resistant foam material according to example 5 of the present invention.

Detailed Description

The invention provides a super-elastic fatigue-resistant foaming material which comprises the following components in parts by weight:

100 parts of thermoplastic elastomer resin, 0.5-50 parts of amorphous metal powder, 0.2-1 part of antioxidant, 0-1.5 parts of stearic acid and 0-1 part of foam stabilizer.

Compared with the prior art, the superelastic fatigue-resistant material provided by the invention adopts specific content components, so that better interaction is realized; the product has ultrahigh resilience characteristic and good compression deformation resistance, thereby obviously improving energy feedback and having a durable cushioning function.

In the invention, the super elastic fatigue resistant foaming material comprises 100 parts of thermoplastic elastomer resin; the thermoplastic elastomer resin is preferably selected from Thermoplastic Polyurethane (TPU), nylon elastomer (TPAE), thermoplastic polyester elastomer (TPEE), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-ethylene/propylene-styrene block copolymer (SEPS), ethylene-Octene Block Copolymer (OBC), ethylene-octene random copolymer (POE), Ethylene Vinyl Acetate (EVA), thermoplastic vulcanizate elastomer (TPV), trans-1, 4-polyisoprene rubber (TPI), syndiotactic 1,2 polybutadiene (TBI), polyvinyl chloride (PVC), Thermoplastic Chlorinated Polyethylene (TCPE), One or more of Polydimethylsiloxane (PDMS) and organic fluorine-based thermoplastic elastomer (TPF), more preferably one or two of Thermoplastic Polyurethane (TPU), nylon elastomer (TPAE), thermoplastic polyester elastomer (TPEE), and Ethylene Vinyl Acetate (EVA). The source of the thermoplastic elastomer resin in the present invention is not particularly limited, and the above-mentioned thermoplastic elastomer resins known to those skilled in the art may be used, and commercially available products thereof may be used, or they may be prepared by themselves. The thermoplastic elastomer resin is adopted as a main raw material, the hardness of the thermoplastic elastomer resin is preferably 50 Shore A-55 Shore D, more preferably 70 Shore A-90 Shore A, the melt index is preferably 1g/10 min-30 g/10min (190 ℃/2.16kg), the Vicat softening temperature is preferably 40-150 ℃, and the elongation at break is preferably more than 200%; the thermoplastic elastomer resin has high mechanical property, good elasticity and good fatigue resistance.

In the invention, the super-elastic fatigue-resistant foaming material comprises 0.5-50 parts of amorphous metal powder, preferably 1-6 parts. The amorphous metal powder is selected from one or more of iron (Fe) -based alloy, nickel (Ni) -based alloy, aluminum (Al) -based alloy, zirconium (Zr) -based alloy, cobalt (Co) -based alloy, copper (Cu) -based alloy, titanium (Ti) -based alloy, magnesium (Mg) -based alloy, calcium (Ca) -based alloy, platinum (Pb) -based alloy, palladium (Pb) -based alloy, gold (Au) -based alloy, hafnium (Hr) -based alloy, and rare earth-based alloy (e.g., La, Nd, Ce) powder. In a specific embodiment, the amorphous metal powder is selected from the group consisting of 1: 1 of nickel titanium alloy; or an iron-based alloy comprising Fe 60%, Ni 15%, Cr 18%, B4%, the other 3%; or an aluminum-based alloy comprising 8 wt% Ni,6 wt% Y, 5 wt% Co,3 wt% La, and the balance Al78 wt%. In the present invention, the amorphous metal powder is mainly used as a filler, dispersed in the matrix to facilitate nucleation and crystallization and to improve the strength of the resin, as well as to increase the elasticity of the resin. In the invention, the amorphous metal powder preferably adopts a micro-nano nucleating agent, the energy barrier between micro-nano nucleating agent particles and a polymer melt interface is low, and the nucleation of foam cells is easy to occur around the particles, so that the nucleation process is promoted, the size of the foam cells is greatly reduced, and the density of the foam cells is improved; the size of the micro-nano nucleating agent is preferably less than 50 μm, and more preferably less than 20 μm.

In the invention, the super-elastic fatigue-resistant foaming material comprises 0.2-1 part of antioxidant, preferably 0.2-0.8 part, and more preferably 0.3 part. The antioxidant is selected from hindered phenol antioxidants, more preferably from AT-10 and/or AT-3114; in a preferred embodiment of the invention, the antioxidant is AT-10. The source of the antioxidant is not particularly limited in the present invention, and commercially available products of the above hindered phenol antioxidants known to those skilled in the art may be used.

In the invention, the thermoplastic elastomer composite material comprises 0-1.5 parts of stearic acid, preferably 0.4-0.7 parts, and more preferably 0.5 parts. The stearic acid is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.

The thermoplastic elastomer composite material comprises 0-1 part of a foam stabilizer, preferably 0.1-0.7 part, and more preferably 0.3-0.5 part. In the present invention, the cell stabilizer is preferably an acrylic substance, more preferably polyisobutyl methacrylate and/or polybutyl methacrylate; in a preferred embodiment of the invention, the cell stabilizer is polyisobutyl methacrylate. The present invention is not particularly limited as to the source of the cell stabilizer, and any commercially available acrylic known to those skilled in the art can be used.

In the invention, the addition of the antioxidant, the stearic acid and the foam hole stabilizer is beneficial to forming and processing and improves the product performance; wherein, the addition of the antioxidant and the stearic acid can improve the processing stability of the composite material; the addition of the cell stabilizer can inhibit the shrinkage of the thermoplastic elastomer resin foaming material and improve the expansion ratio of the material, thereby ensuring that the prepared material has better compression permanent deformation resistance.

According to the super-elastic fatigue-resistant material provided by the invention, the specific content of the components is adopted, a cross-linking agent is not required to be added, the prepared foaming material can be recycled, and a good interaction is realized; the product has ultrahigh resilience characteristic and good compression deformation resistance characteristic, thereby greatly improving energy feedback and having a durable cushioning function.

The invention provides a preparation method of the superelastic fatigue-resistant foam material in the technical scheme, which comprises the following steps:

a) premixing 100 parts of thermoplastic elastomer resin, 0.5-50 parts of amorphous metal powder, 0.2-1 part of antioxidant, 0-1.5 parts of stearic acid and 0-1 part of foam stabilizer, melting and mixing, extruding and granulating to obtain thermoplastic elastomer composite particles;

b) preheating the thermoplastic elastomer composite particles obtained in the step a), putting the thermoplastic elastomer composite particles into a mold, closing the mold, placing the mold in a closed container, introducing gas into the container, heating the container to ensure that the gas reaching a supercritical state soaks and saturates the thermoplastic elastomer composite particles, and finally quickly relieving the pressure and opening the mold to obtain the super-elastic fatigue-resistant foaming material;

or extruding the thermoplastic elastomer composite particles obtained in the step a) into a plate by a double screw or injecting the plate into a special-shaped part with a 3D structure; and (3) soaking the sheet or the special-shaped part in a high-pressure fluid atmosphere until the sheet or the special-shaped part is balanced, and then quickly relieving pressure to obtain the super-elastic fatigue-resistant foaming material.

The method provided by the invention is simple, mild in condition, short in flow, high in efficiency and suitable for large-scale industrial production.

The invention firstly mixes all components in the thermoplastic elastomer composite material in advance, then carries out melt mixing, and cuts the granules after extrusion to obtain the thermoplastic elastomer composite granules. In the present invention, the thermoplastic elastomer composite material is the same as that in the above technical solution, and is not described herein again.

In the present invention, the apparatus for melt kneading and extrusion is preferably an extruder, and the present invention is not particularly limited thereto. In the invention, the temperature of the melt mixing is preferably 130 to 210 ℃, and more preferably 190 to 200 ℃; the time for the melt kneading is preferably 1 to 10min, more preferably 1 to 5 min.

In the invention, the granulating mode is preferably underwater granulating; the temperature of water in the underwater pelletizing process is preferably 15 ℃ to 35 ℃, and more preferably 25 ℃.

After the thermoplastic elastomer composite particles are obtained, the obtained thermoplastic elastomer composite particles are preheated and then are filled into a mold to be closed, the mold is placed in a closed container, gas is introduced into the container, the temperature is raised, the thermoplastic elastomer composite particles are soaked and saturated by the gas reaching a supercritical state, and finally, the pressure is quickly released and the mold is opened, so that the super-elastic fatigue-resistant foaming material is obtained. In the present invention, the temperature of the preheating is preferably 40 to 130 ℃, more preferably 80 to 120 ℃.

In the present invention, the present invention is not particularly limited to the mold. Before the thermoplastic elastomer composite particles obtained in the present invention are loaded into a mold, it is preferable that the method further comprises:

preheating the mold to a temperature at which the thermoplastic elastomer composite particles are preheated.

In the present invention, the closed vessel is preferably an autoclave; the present invention is not particularly limited in this regard.

In the present invention, the gas is preferably carbon dioxide gas or nitrogen gas, and more preferably carbon dioxide gas. In the present invention, the impregnation saturation means impregnation under an atmosphere with a high pressure fluid until the high pressure fluid and the blank member reach a dissolution equilibrium. In the invention, the temperature for impregnation saturation is preferably 80-190 ℃, and more preferably 130-160 ℃; the impregnation saturation pressure is preferably 5MPa to 50MPa, more preferably 10MPa to 40MPa, and most preferably 15MPa to 20 MPa; the time for the impregnation saturation is preferably 3min to 50min, and more preferably 5min to 40 min.

In the invention, the rapid pressure relief rate is preferably 5MPa/s to 30MPa/s, more preferably 8MPa/s to 25MPa/s, and most preferably 15 MPa/s.

According to the invention, by utilizing a supercritical fluid kettle pressure method, the thermoplastic elastomer composite particles are impregnated in a high-pressure fluid atmosphere until the high-pressure fluid and the resin reach a dissolution balance, and the resin is rapidly expanded to a predetermined density through rapid pressure relief, so that the ultralight high-elasticity foaming material with the 3D structure is prepared. In the invention, the supercritical fluid is foamed by a kettle pressure method, carbon dioxide or nitrogen is injected into a kettle containing an elastomer composite material, the supercritical state is achieved after the carbon dioxide or nitrogen reaches a certain temperature and pressure, the state is maintained for a certain time, the supercritical fluid permeates into the raw material of the elastomer composite to form a polymer/gas homogeneous system, the balance state of the polymer/gas homogeneous system in the material is destroyed by a rapid depressurization method, and bubble nuclei are formed in the material and grow and are shaped to obtain a foamed material; wherein, increasing the gas pressure can improve the solubility of the gas in the polymer, thereby increasing the nucleation number of bubbles and increasing the cell density; the pressure drop is increased, and the faster the bubble nucleation rate is, the more bubble nuclei are; the gas concentration gradient inside and outside the bubble or the pressure difference inside and outside the bubble is the motive power for driving the bubble to grow, the pressure relief rate directly reflects the acceleration of the bubble growth, and the increase of the pressure relief rate is beneficial to the reduction of the diameter of the bubble and the increase of the density of the bubble; above the glass transition temperature, the lower the saturation temperature, the higher the solubility of carbon dioxide in the polymer, the higher the nucleation rate and the higher the nucleation density.

The invention adopts the preparationThe method comprises the step of subjecting thermoplastic elastomer composite particles to a supercritical fluid foaming molding process (the thermoplastic elastomer composite particles are prepared by one-step quick pressure relief foaming after supercritical fluid impregnation), so as to prepare the super-elastic fatigue-resistant foaming material, wherein the foaming material is a polymer foam material with a 3D structure, and the density of the foaming material is lower than 0.2g/cm³The sole can be applied to the insole of sports shoes, so that the shoes have lighter weight, the rebound rate of the shoes is more than 70%, the rebound resilience is high, the shoes have excellent fatigue resistance, and better comfortable experience can be provided for shoe wearers; meanwhile, the preparation method has the advantages of simple process, mild conditions, short production flow and high efficiency, and is suitable for large-scale industrial production.

Compared with the prior art, the traditional ETPU foaming shoe material manufacturing process comprises the steps of ETPU bead preparation and steam forming, and the foamed particles are compressed into a mould to obtain the insole, so that the method is difficult to realize the lightening of the insole; the method has the advantages that the particles can realize free foaming, the expansion rate is higher, and the insole product can be obtained after the expansion is filled in a mould, so that the insole can be lightened; in addition, compared with the existing EVA foaming shoe material, the super-elastic fatigue-resistant foaming material prepared by the preparation method provided by the invention has the advantages of equivalent hardness, non-crosslinking recoverability, high resilience and low compression permanent deformation, and compared with the traditional steam forming ETPU foaming shoe material, the super-elastic fatigue-resistant foaming material has the advantages of high efficiency, light weight, high resilience and low compression permanent deformation, and has lasting comfort and lasting shock absorption functions, so that a runner can have good running experience.

The super-elastic fatigue-resistant foaming material provided by the invention can be applied to the fields of sports shoe soles, midsoles, automobile cushions, sports equipment retarding cushions and the like.

In order to further illustrate the present invention, the following examples are provided to describe a super elastic fatigue resistant foaming material and its preparation method and application in detail, but they should not be construed as limiting the scope of the present invention.

The Thermoplastic Polyurethane (TPU) used in the following examples of the invention has a hardness of about 85A, a melt flow rate of 15g/10min (200 ℃/3.8kg), a Vicat softening temperature of 72 ℃, and an elongation at break of 600%; the used thermoplastic polyester elastomer (TPEE) has the hardness of Shore 40D, the melt flow rate of 5g/10min (190 ℃/2.16kg), the Vicat softening temperature of more than or equal to 105 ℃, and the elongation at break of more than 400 percent; the used nylon elastomer (TPAE) has the hardness of Shore 40D, the melt flow rate of 4g/10min (190 ℃/2.16kg), the Vicat softening temperature of more than or equal to 125 ℃, and the elongation at break of more than 200 percent; the used Ethylene Vinyl Acetate (EVA) has the hardness of 83A, the melt flow rate of 3g/10min (190 ℃/2.16kg), the Vicat softening temperature of 46 ℃ and the elongation at break of more than or equal to 800 percent; the viscosity of the used cell stabilizer is 0.6 pas-1.2 pas; the amorphous metal alloy powder used has a size below 20 μm.

Example 1

(1) The thermoplastic elastomer composite material comprises the following components in percentage by weight:

thermoplastic Polyurethane (TPU): 100 parts by weight;

amorphous metal alloy powder: 5 parts by weight;

antioxidant: 0.3 part by weight;

stearic acid: 0.5 part by weight;

cell stabilizer: 0.5 part by weight;

wherein the amorphous metal alloy powder is nickel-titanium alloy (nickel and titanium respectively account for 50%); the antioxidant is AT-10; the cell stabilizer is polyisobutyl methacrylate.

(2) The preparation method comprises the following steps:

weighing the components in the thermoplastic elastomer composite material as raw materials in parts by weight; premixing the weighed raw materials, melting and mixing for 5min at 200 ℃ by using an extruder, and granulating under water at 25 ℃ after extrusion to obtain thermoplastic elastomer composite particles; then preheating the obtained thermoplastic elastomer composite particles to 100 ℃, pouring the thermoplastic elastomer composite particles into a mold which is also preheated to 100 ℃, closing the mold, putting the mold into a closed container, introducing nitrogen into the container, heating to 140 ℃ (the pressure is 15MPa), so that the thermoplastic elastomer composite particles are impregnated and saturated by gas reaching a supercritical state for 30min, then quickly relieving the pressure (the pressure relief rate is 15MPa/s) and opening the mold to obtain the super-elastic fatigue-resistant material;

fig. 1 is a top view of a super elastic fatigue resistant foamed material provided in example 1 of the present invention.

Internal cell structure of material referring to fig. 2, wherein the upper side is a structure view of internal cells of the material prepared in comparative example 1 and the lower side is a structure view of internal cells of the material prepared in example 1.

Example 2

(1) The thermoplastic elastomer composite material comprises the following components in percentage by weight:

thermoplastic polyester elastomer (TPEE): 100 parts by weight;

amorphous metal alloy powder: 5 parts by weight;

antioxidant: 0.3 part by weight;

stearic acid: 0.5 part by weight;

cell stabilizer: 0.5 part by weight;

wherein the amorphous metal alloy powder is iron-based alloy (Fe 60%, Ni 15%, Cr 18%, B4%, and the rest 3%); the antioxidant is AT-10; the nucleating agent is nano titanium dioxide; the cell stabilizer is polyisobutyl methacrylate.

(2) The preparation method comprises the following steps:

weighing the components in the thermoplastic elastomer composite material as raw materials in parts by weight; premixing the weighed raw materials, melting and mixing for 5min at 195 ℃ by using an extruder, and granulating under water at 25 ℃ after extrusion to obtain thermoplastic elastomer composite particles; then preheating the obtained thermoplastic elastomer compound particles to 120 ℃, pouring the thermoplastic elastomer compound particles into a midsole mold preheated to 120 ℃ as well, closing the mold, putting the mold into a closed container, introducing nitrogen gas into the container, heating to 160 ℃ (the pressure is 15MPa), so that the thermoplastic elastomer compound particles are impregnated and saturated by the gas reaching the supercritical state for 25min, then quickly relieving the pressure (the pressure relief rate is 15MPa/s) and opening the mold to obtain the superelastic fatigue-resistant material; as shown in fig. 3.

Example 3

(1) The thermoplastic elastomer composite material comprises the following components in percentage by weight:

thermoplastic Polyurethane (TPU): 100 parts by weight;

amorphous metal alloy powder: 5 parts by weight;

antioxidant: 0.3 part by weight;

stearic acid: 0.5 part by weight;

cell stabilizer: 0.5 part by weight;

wherein the amorphous alloy powder is aluminum-based alloy (8 wt% of Ni,6 wt% of Y, 5 wt% of Co,3 wt% of La, and the balance of Al78 wt%); the antioxidant is AT-10; the cell stabilizer is polyisobutyl methacrylate.

(2) The preparation method comprises the following steps:

weighing the components in the thermoplastic elastomer composite material as raw materials in parts by weight; premixing the weighed raw materials, melting and mixing for 5min at 190 ℃ by using an extruder, and granulating under water at 25 ℃ after extrusion to obtain thermoplastic elastomer composite particles; adding the obtained thermoplastic elastomer composite particles into a 190 ℃ double screw to extrude into sheets, putting the sheets into a pressure kettle, introducing nitrogen gas into the kettle, heating to 140 ℃ (the pressure is 15MPa), so that the thermoplastic elastomer composite is impregnated and saturated by the gas reaching the supercritical state for 90min, then quickly relieving the pressure (the pressure relief rate is 15MPa/s) and opening the kettle to obtain the super-elastic fatigue-resistant material; as shown in fig. 4.

Example 4

(1) The thermoplastic elastomer composite material comprises the following components in percentage by weight:

nylon elastomer (TPAE): 100 parts by weight;

amorphous metal alloy powder: 5 parts by weight;

antioxidant: 0.3 part by weight;

stearic acid: 0.5 part by weight;

cell stabilizer: 0.3 part by weight;

wherein the amorphous metal alloy powder is nickel-titanium alloy (nickel and titanium respectively account for 50%); the antioxidant is AT-10; the cell stabilizer is polyisobutyl methacrylate.

(2) The preparation method comprises the following steps:

weighing the components in the thermoplastic elastomer composite material as raw materials in parts by weight; premixing the weighed raw materials, melting and mixing for 5min at 200 ℃ by using an extruder, and granulating under water at 25 ℃ after extrusion to obtain thermoplastic elastomer composite particles; then preheating the obtained thermoplastic elastomer compound particles to 120 ℃, pouring the thermoplastic elastomer compound particles into a midsole mold preheated to 120 ℃ as well, closing the mold, putting the mold into a closed container, introducing nitrogen gas into the container, heating to 140 ℃ (the pressure is 27MPa), so that the thermoplastic elastomer compound particles are impregnated and saturated by the gas reaching the supercritical state for 25min, then quickly relieving the pressure (the pressure relief rate is 15MPa/s) and opening the mold to obtain the superelastic fatigue-resistant material; as shown in fig. 5.

Example 5

(1) The thermoplastic elastomer composite material comprises the following components in percentage by weight:

thermoplastic Polyurethane (TPU): 60 parts by weight;

ethylene Vinyl Acetate (EVA): 40 parts by weight;

amorphous metal alloy powder: 5 parts by weight of

Antioxidant: 0.3 part by weight;

stearic acid: 0.5 part by weight;

cell stabilizer: 0.5 part by weight;

wherein the amorphous metal alloy powder is iron-based alloy (Fe 60%, Ni 15%, Cr 18%, B4%, and the rest 3%); the antioxidant is AT-10; the cell stabilizer is polyisobutyl methacrylate.

(2) The preparation method comprises the following steps:

weighing the components in the thermoplastic elastomer composite material as raw materials in parts by weight; premixing the weighed raw materials, melting and mixing for 5min at 190 ℃ by using an extruder, and granulating under water at 25 ℃ after extrusion to obtain thermoplastic elastomer composite particles; adding the obtained thermoplastic elastomer composite particles into a double screw at 190 ℃, injecting the particles into a mold to obtain a 3D-structured special-shaped part, putting the special-shaped part into a pressure kettle, introducing nitrogen gas into the kettle, heating to 140 ℃ (the pressure is 15MPa), allowing the gas reaching a supercritical state to perform impregnation saturation on the thermoplastic elastomer composite for 90min, then quickly relieving the pressure (the pressure relief rate is 15MPa/s), and opening the kettle to obtain the super-elastic fatigue-resistant material; as shown in fig. 6.

Comparative example 1

(1) The thermoplastic elastomer composite material comprises the following components in percentage by weight:

thermoplastic Polyurethane (TPU): 100 parts by weight;

antioxidant: 0.3 part by weight;

stearic acid: 0.5 part by weight;

cell stabilizer: 0.5 part by weight;

wherein the antioxidant is AT-10; the cell stabilizer is polyisobutyl methacrylate.

(2) The preparation method comprises the following steps:

weighing the components in the thermoplastic elastomer composite material as raw materials in parts by weight; premixing the weighed raw materials, melting and mixing for 5min at 200 ℃ by using an extruder, and granulating under water at 25 ℃ after extrusion to obtain thermoplastic elastomer composite particles; then preheating the obtained thermoplastic elastomer composite particles to 100 ℃, pouring the thermoplastic elastomer composite particles into a mold which is also preheated to 100 ℃, closing the mold, putting the mold into a closed container, introducing nitrogen into the container, heating to 140 ℃ (the pressure is 15MPa), so that the thermoplastic elastomer composite particles are impregnated and saturated by gas reaching a supercritical state for 30min, then quickly relieving the pressure (the pressure relief rate is 15MPa/s) and opening the mold to obtain the super-elastic fatigue-resistant material; see the left diagram in fig. 2.

The invention carries out performance test on the super-elastic fatigue-resistant foaming materials prepared in examples 1-5 and comparative example 1, and the results are shown in Table 1:

TABLE 1 results of Performance test of materials prepared in examples 1-5 and comparative example 1

As can be seen from table 1, the superelastic fatigue-resistant materials provided in embodiments 1 to 5 of the present invention have ultrahigh resilience, good compression deformation resistance, and excellent mechanical properties, and have ultrahigh energy feedback and a durable cushioning function; in addition, comparing examples 1-5, it can be seen that different resins can be used to obtain materials with different densities, with example 4 having the lowest density and the highest rebound resilience; comparing example 1 and example 2, it can be seen that blending TPEE resin results in a lower density, higher resilience material than pure TPU resin foam; comparing example 1 and example 5, it can be seen that blending EVA resin can result in a material with better hand (lower stiffness) than pure TPU resin foam; comparing example 1 with comparative example 1, it can be seen that blending amorphous metal alloy powder can significantly improve the resilience, fatigue resistance and tensile strength of the material, as well as the hardness of the material.

According to the embodiment, the invention provides a super-elastic fatigue-resistant foaming material which comprises, by weight, 100 parts of thermoplastic elastomer resin, 0.5-50 parts of amorphous metal powder, 0.2-1 part of antioxidant, 0-1.5 parts of stearic acid and 0-1 part of foam stabilizer. Compared with the prior art, the super-elastic fatigue-resistant foaming material provided by the invention adopts specific materials and content components, so that better interaction is realized; the product has light density, super high resilience characteristic and excellent compression deformation resistance characteristic to when promoting sports shoes elasticity greatly, have lasting comfortable and lasting shock-absorbing function concurrently, give the person of dress good and the experience of running.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.