CN113402876B - Super-elastic fatigue-resistant foam material and preparation method and application thereof - Google Patents
Super-elastic fatigue-resistant foam material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
- A43B13/18—Resilient soles
- A43B13/187—Resiliency achieved by the features of the material, e.g. foam, non liquid materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
- B60N2/00—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles
- B60N2/62—Thigh-rests
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Abstract
The invention provides a super-elastic fatigue-resistant foaming material and a preparation method and application thereof, wherein the material 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.
Description
Technical Field
The invention belongs to the technical field of foam manufacturing, and particularly relates to a super-elastic fatigue-resistant foaming material, and a preparation method and application thereof.
Background
High elasticity foams have a wide range of applications, particularly in the sporting goods industry, such as in the midsole material of sports shoes, which is the core technology of shoes, has the effects of reducing impact when falling to the ground, providing forward propulsion, safety protection and comfort, and are generally foams of thermoplastic elastomers, mainly related 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, in which thermoplastic elastomer materials such as EVA and polyolefin block copolymer (OBC) are used as a main matrix, and supercritical foaming is performed 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 the 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 cross-linked foamed high-elastic wear-resistant ultra-light sports shoe sole material with polyether block amide as a matrix and a preparation method thereof, wherein the foaming is performed by a chemical foaming agent, so that the ultra-light of the cross-linked foamed shoe sole material is realized, and the requirements of high elasticity, buffering, shock absorption and wear resistance are met. 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 meanwhile, a fiber reinforced filler is 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, trans-1, 4-polyisoprene rubber, syndiotactic 1,2 polybutadiene, polyvinyl chloride, thermoplastic chlorinated polyethylene, polydimethylsiloxane and organic fluorine-based 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, carrying out melt mixing, and granulating after extrusion to obtain thermoplastic elastomer composite particles;
b) preheating the thermoplastic elastomer composite particles obtained in the step a), filling the preheated 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 supercritical gas soaks and saturates the thermoplastic elastomer composite particles, and finally quickly relieving pressure and opening the mold to obtain the superelastic fatigue-resistant foam material;
or extruding the thermoplastic elastomer composite particles obtained in the step a) into a plate by a double screw or injecting 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 superelasticity 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 superelastic fatigue-resistant foam material according to 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 having the durable cushioning function while obviously improving energy feedback.
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 (TPEE), 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 one or more selected from the group consisting 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 can 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 commercially available products of the above-mentioned acrylic materials well known to those skilled in the art can be used.
In the invention, the addition of the antioxidant, stearic acid and the foam stabilizer is beneficial to molding 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.
The super-elastic fatigue-resistant material provided by the invention adopts the components with specific contents, and a cross-linking agent is not required to be added, so that 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 super-elastic fatigue-resistant foam material, 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), filling the preheated 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 supercritical gas soaks and saturates the thermoplastic elastomer composite particles, and finally quickly relieving pressure and opening the mold to obtain the superelastic fatigue-resistant foam 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 decompression 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, a supercritical fluid kettle pressure method is utilized to impregnate the thermoplastic elastomer composite particles 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 preset density through rapid pressure relief, so that the ultralight high-elasticity foaming material with a 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 greater the nucleation density.
According to the preparation method, the thermoplastic elastomer composite particles are subjected to a supercritical fluid foaming molding process (the thermoplastic elastomer composite particles are prepared by one step of rapid pressure relief and foaming after supercritical fluid impregnation), so that the super-elastic fatigue-resistant foaming material is prepared, and the foaming material is a polymer foam material with a 3D structure, and has a lower density which 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 foamed shoe material, the superelastic fatigue-resistant foamed 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, has the advantages of high efficiency, light weight, high resilience and low compression permanent deformation compared with the traditional steam forming ETPU foamed shoe material, has lasting comfort and lasting shock absorption functions, and gives a runner 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 slow-down 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 Shore 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 foam stabilizer is 0.6 Pa.s-1.2 Pa.s; 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, placing the mold into a closed container, introducing nitrogen into the container, heating to 140 ℃ (the pressure is 15MPa), allowing the gas reaching a supercritical state to perform impregnation saturation on the thermoplastic elastomer composite particles for 30min, then quickly relieving the pressure (the pressure relief rate is 15MPa/s) and opening the mold to obtain the superelastic 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; preheating the obtained thermoplastic elastomer compound particles to 120 ℃, pouring the thermoplastic elastomer compound particles into a midsole mold preheated to 120 ℃ in the same way, closing the mold, putting the mold into a closed container, introducing nitrogen gas into the container, heating to 160 ℃ (the pressure is 15MPa), allowing the gas reaching a supercritical state to dip and saturate the thermoplastic elastomer compound particles 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 ℃ twin-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 pressure (the pressure relief rate is 15MPa/s), and opening the kettle to obtain the superelastic 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 particles into a midsole mold preheated to 120 ℃ in the same way, closing the mold, putting the mold into a closed container, introducing nitrogen gas into the container, heating the container to 140 ℃ (the pressure is 27MPa), allowing the gas reaching a supercritical state to dip and saturate the thermoplastic elastomer compound particles 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 structural 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), soaking and saturating the thermoplastic elastomer composite by the gas reaching a supercritical state for 90min, then quickly relieving pressure (the pressure relief rate is 15MPa/s) and opening the kettle to obtain the superelasticity 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, placing the mold into a closed container, introducing nitrogen into the container, heating to 140 ℃ (the pressure is 15MPa), allowing the gas reaching a supercritical state to perform impregnation saturation on the thermoplastic elastomer composite particles for 30min, then quickly relieving the pressure (the pressure relief rate is 15MPa/s) and opening the mold to obtain the superelastic 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 Performance test results for 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 an ultrahigh resilience, a good compression deformation resistance, and excellent mechanical properties, and have an 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 foaming; 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 the following components, 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, ultrahigh resilience characteristic and excellent compression deformation resistance characteristic, thereby greatly improving the elasticity of the sports shoe, having lasting comfort and lasting shock absorption function, and providing good wearing and running experience for a wearer.
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 amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. The 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;
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.
2. The superelastic fatigue-resistant foam material of 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.
3. A method for preparing the superelastic fatigue-resistant foam material according to any one of claims 1-2, 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, carrying out melt mixing, and granulating after extrusion to obtain thermoplastic elastomer composite particles;
b) preheating the thermoplastic elastomer composite particles obtained in the step a), filling the preheated 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 supercritical gas soaks and saturates the thermoplastic elastomer composite particles, and finally quickly relieving pressure and opening the mold to obtain the superelastic fatigue-resistant foam 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.
4. The method according to claim 3, wherein the temperature of the melt-kneading in the step a) is 130 to 210 ℃ and the time is 1 to 10 min.
5. The method according to claim 3, wherein the screw temperature for the extruding or ejecting in the step b) is 100 to 200 ℃.
6. The preparation method according to claim 3, 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.
7. The preparation method of claim 3, wherein the rapid pressure relief rate in the step b) is 5-30 MPa/s.
8. The application of the superelastic fatigue-resistant foam material according to any one of claims 1-2 or the superelastic fatigue-resistant foam material prepared by the preparation method according to any one of claims 3-7 in a sports shoe sole midsole, an automobile cushion or a sports equipment shock pad.
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