CN110776724A - Functional elastic foaming material and preparation method and application thereof - Google Patents

Functional elastic foaming material and preparation method and application thereof Download PDF

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CN110776724A
CN110776724A CN201911013298.9A CN201911013298A CN110776724A CN 110776724 A CN110776724 A CN 110776724A CN 201911013298 A CN201911013298 A CN 201911013298A CN 110776724 A CN110776724 A CN 110776724A
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functional elastic
mixing
foaming
plate
weight
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CN110776724B (en
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张振秀
韩迎霞
张昕
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Qingdao University of Science and Technology
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Qingdao University of Science and Technology
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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
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon

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  • Polymers & Plastics (AREA)
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Abstract

The invention provides a functional elastic foaming material and a preparation method and application thereof. The invention comprises the following steps: 1) taking 60-100 parts by weight of thermoplastic polyester elastomer and 0-40 parts by weight of ethylene-vinyl acetate copolymer and/or thermoplastic polyurethane elastomer rubber as raw materials, and mixing; 2) mixing, forming and crosslinking to obtain a plate; 3) supercritical nitrogen intermittent risingFoaming at a temperature of 16-30MPa, 80-120 deg.C, 4-8h, 1-15s, and at 180 deg.C for 5-30min to obtain the functional elastic foam material. The invention adopts supercritical nitrogen gas to intermittently heat and foam, the product size is not limited, the equipment is simple, the process is simple and environment-friendly, and the density of the obtained product is 0.08-0.18g/cm 3The ball has light weight, ultrahigh rebound resilience of 76-85% and wide application range.

Description

Functional elastic foaming material and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a functional elastic foaming material and a preparation method and application thereof.
Background
Thermoplastic polyester elastomer (TPEE) is also called polyester rubber, is a linear block copolymer containing PBT (polybutylene terephthalate) polyester hard segment and aliphatic polyester or polyether soft segment, and the hard segment has high hardness and crystallinity; the soft segment is usually selected from non-crystalline Tg polyether (such as polyethylene glycol ether PEG, polypropylene glycol ether PPG, polytetramethylene glycol ether PTMG, etc.) or polyester (such as aliphatic polyester of polylactide PLLA, polyglycolide PGA, polycaprolactone PCL, etc.). The soft polyether segment and the uncrystallized polyester form an amorphous phase, and the hard polyester segment is partially crystallized to form crystalline domains which function as physical crosslinking points. TPEE has the elasticity of rubber and the strength of engineering plastics, and the soft segment gives it elasticity, making it like rubber; the hard segment gives it processability, making it like plastic; compared with rubber, the rubber has better processing performance and longer service life; compared with engineering materials, the material has the characteristics of high strength, and better flexibility and dynamic mechanical property.
The existing foaming materials in the market are mostly chemically foamed, for example: chinese patent CN104672788A discloses a micro-crosslinked modified polyester elastomer micro-foaming material and a preparation method thereof in 2018, 6.3.8.A thermoplastic polyester elastomer is taken as a raw material, a microcapsule foaming agent or a chemical foaming agent is added into the thermoplastic polyester elastomer, and the micro-crosslinked modified polyester elastomer micro-foaming material is prepared by electron beam irradiation crosslinking or modification by a chemical crosslinking agent. The product obtained by the foaming method adopting the chemical foaming agent has the by-product residue and large pollution, so that the application range of the product is limited. Secondly, there are also some bead foaming methods in the prior art, such as: chinese patent CN109080061A discloses a casting molding process of thermoplastic elastomer foamed particles in 2018, 12 and 25.s, the foaming molding process uses thermoplastic elastomer foamed particles with a closed pore structure and an open pore structure extending to the skin as raw materials, then the raw materials of the thermoplastic elastomer foamed particles are filled into a molding die, and a reaction type polyurethane adhesive is poured, hot-pressed, cooled and molded to obtain a molded product; the process needs to screen the foaming beads, is long in time consumption, has narrow range of applicable materials for steam forming, has poor steam forming cohesiveness of TPEE particles, and has large density of the formed plate, thereby influencing light-weight production. In addition, some extrusion foaming processes exist in the prior art, and Chinese patent CN108864662A discloses a thermoplastic polyether ester elastomer foaming material and a preparation method thereof, wherein the preparation method comprises the steps of melting and uniformly mixing an elastomer raw material, an auxiliary agent and a foaming agent in an extruder, extruding the mixture into a specific mould, and cooling and shaping the mixture; although the method can continuously produce the foamed sheet, the method has strict processing requirements on raw materials, namely, enough melt strength needs to be ensured to avoid the melt from being punctured by a gas core expanding at a high speed, the equipment investment is large, and the quantity of produced products is limited.
Disclosure of Invention
The invention aims to provide a functional elastic foaming material, a preparation method and application thereof, and solves the problems of large pollution, long time consumption, large density, large equipment investment and limited number of produced products in the preparation method of the thermoplastic polyester elastomer foaming material in the prior art.
In order to solve the technical problem, the technical scheme of the invention is realized as follows:
in one aspect, the present invention provides a method for preparing a functional elastic foam material, comprising the steps of:
1) mixing raw materials including 60-100 parts by weight of thermoplastic polyester elastomer and 0-40 parts by weight of ethylene-vinyl acetate copolymer and/or thermoplastic polyurethane elastomer rubber to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), and forming and crosslinking to obtain a plate;
3) and (3) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 2), wherein the saturation pressure is 16-30MPa, the saturation temperature is 80-120 ℃, the saturation time is 4-8h, the pressure relief time is 1-15s, and foaming is carried out for 5-30min at the temperature of 150 ℃ and 180 ℃ to obtain the functional elastic foaming material.
The lightweight high-elasticity plate is directly obtained by taking the thermoplastic polyester elastomer (TPEE) or the mixture of the thermoplastic polyester elastomer (TPEE) and any one or two of ethylene-vinyl acetate copolymer (EVA) and thermoplastic polyurethane elastomer rubber (TPU) as a raw material and adopting a supercritical nitrogen intermittent heating foaming method, the product size is not limited, the equipment is simple, no chemical foaming agent is used, the process is simple, convenient and environment-friendly, the operation is convenient, the production efficiency is high, and the production cost is low; the density of the obtained product is 0.08-0.18g/cm 3The ball has very light weight and ultrahigh rebound resilience, and the rebound resilience of the falling ball is between 76 and 85 percent.
As a preferred embodiment, said step 1) and said step 2) further comprise, after said step 1) and before said step 2): adding an antistatic agent into the primary mixture, and continuously mixing to obtain a mixture; the addition amount of the antistatic agent is 5-12%. By adding the antistatic agent, an ultra-light, compression-resistant and antistatic foam material can be obtained, and the application range is further expanded.
As a preferred embodiment, the antistatic agent is any one of graphene, carbon nanotubes, carbon fibers, conductive carbon black and metal fibers. The antistatic agents of the invention have good use effect, wide sources, low price and easy obtainment.
As a preferred embodiment, said step 2) and said step 3) further comprise, after said step 2) and before said step 3): a) mixing chloroform, an organic solvent and an organic pigment according to a mass ratio of 8-12:20:1 to prepare a dye for later use; b) and (c) coating the dye obtained in the step a) on the plate obtained in the step 2) by using a brush or a pen. The invention can also utilize dye to draw patterns, produce any pattern, utilize the swelling principle of crosslinked polymer, adopt the board of any relief pattern of one-step manufacture of supercritical method, through the control of saturation time, can adjust the relief thickness of the foamed product, can also come from density and relief effect of the independent regulation board through saturation time and saturation pressure, the flexibility is strong, the operability is simple. The organic solvent of the invention is absolute ethyl alcohol, absolute methyl alcohol, absolute propyl alcohol, acetone and the like, and the organic pigment of the invention is carbon black, phthalocyanine blue, aurora red and the like.
As a preferred embodiment, the surface of the functional elastic foaming material is provided with a relief pattern, and the height of the relief pattern is 0.8-2.0 mm. The invention has obvious relief pattern effect, strong stereoscopic impression, simple and efficient process and low production cost.
As a preferred embodiment, said step 2) and said step 3) further comprise, after said step 2) and before said step 3): A) mixing chloroform, an organic solvent and an organic pigment according to a mass ratio of 20-25:20:1 to prepare a dye for later use; B) and B), coating the dye obtained in the step A) on the plate obtained in the step 2) by using a brush or a pen. The invention can also utilize dye to engrave patterns on the board, engrave any pattern, utilize the swelling principle of crosslinked macromolecules, adopt the supercritical method to manufacture the board with any pattern with engraved effect in one step, can adjust the engraving depth of the foamed product through the control of the saturation time, can also automatically adjust the density and engraving effect of the board through the saturation time and the saturation pressure, and has strong flexibility and simple operability. The organic solvent is also anhydrous ethanol, anhydrous methanol, anhydrous propanol, acetone, etc., and the pigment is also carbon black, phthalocyanine blue, aurora red, etc.
As a preferred embodiment, the surface of the functional elastic foaming material is provided with a carved pattern, and the depth of the carved pattern is 1.0-2.5 mm. The invention has the advantages of obvious pattern engraving effect, strong stereoscopic impression, simple and efficient process and low production cost.
At present, the printing effect is poor due to the general foam printing or the performance of the foam, and the durability is not expected; or the original pattern is not maintained because the printing effect is poor due to the continuous diffusion of the organic printing pigment on the foam. In general, antistatic foams are used either by adding antistatic agents to the raw materials or by coating antistatic agents on the foamed products, although these methods are more practical. However, the foaming ratio is also affected, the requirement for weight reduction of the product is affected, and the mechanical properties such as rebound resilience of the product itself are lowered. The method comprises the steps of firstly, adopting a dye containing a TPEE good solvent to draw a required pattern on the surface of a cross-linked TPEE plate, enabling a solvent coating painted on the surface of the TPEE plate to permeate a certain thickness from the surface of the TPEE plate while a supercritical fluid permeates the TPEE plate in a supercritical foaming process, then heating and foaming the plate subjected to supercritical foaming, improving the activity of a TPEE molecular chain because the TPEE cross-linked molecular chain at the pattern is permeated by the solvent, starting expansion of the pattern part before the surrounding in the expansion process of the plate, and then enabling the pattern to protrude a certain thickness than the surrounding after the shape of the plate is not expanded any more so as to form a relief pattern effect. In short, a certain amount of solvent swells the TPEE material of the pattern part, so that the pattern part has a higher expansion ratio than the surrounding foaming ratio after foaming, and a relief effect is formed. The dye used in the pattern engraving process needs to be further adjusted, and the solvent in the dye is increased, so that the swelling effect of the solvent is further improved; after the cross-linked polymer is swelled by the solvent, the swelling part of the plate can slightly bulge the original pattern along with the temperature rise foaming of the supercritical permeable plate at high temperature, but the swelling action improves the movement capacity of a molecular chain, and the cross-linked polymer chain of the pattern part is difficult to maintain a cellular structure due to a certain solvent amount and the prolonged saturation time, so that the TPEE of the pattern part is melted at high temperature under the higher saturation temperature, thereby destroying the cellular structure of the foam of the relief pattern, and the pattern part is sunken down from the periphery, thereby forming the engraved pattern.
As a preferred embodiment, the mixing temperature is 180-185 ℃, and the mixing time is 3-10 min. The raw materials are usually mixed in an internal mixer, then mixed in the internal mixer, the mixing parameters are controlled, and finally the plate is formed by a forming machine; the plate has the advantages of low density, light weight and high resilience.
In another aspect, the invention provides a functional elastic foam material, which is prepared according to the method for preparing the functional elastic foam material. The density of the functional elastic foaming material obtained by the method is 0.08-0.18g/cm 3The ball has very light weight and ultrahigh rebound resilience, and the rebound resilience of the falling ball is between 76 and 85 percent.
In yet another aspect, the present invention is directed to the use of a functional elastic foam material for use as a midsole material. The functional elastic foaming material has the advantages of low density, light weight, high rebound resilience and wide application range, is particularly suitable for insole materials, and the obtained shoes are comfortable to wear, light and soft in texture, good in rebound resilience and good in protection effect on feet.
Compared with the prior art, the invention has the beneficial effects that: the invention takes the thermoplastic polyester elastomer or the mixture of the thermoplastic polyester elastomer and any one or two of ethylene-vinyl acetate copolymer and thermoplastic polyurethane elastomer rubber as the raw material, adopts the supercritical nitrogen intermittent heating foaming method to directly react in one step to obtain the lightweight high-elastic plate, and the product size is not limited in the production process of the high-elastic plate, the equipment is simple, no chemical foaming agent is used, the process is simple, convenient and environment-friendly, the operation is convenient, the production efficiency is high, and the production cost is low; the density of the obtained product is 0.08-0.18g/cm 3The shoe sole has the advantages of light weight, ultrahigh rebound resilience, wide application range, particular suitability for shoe insole materials, comfortable wearing of the obtained shoe, light and soft texture, good rebound resilience and good protection effect on feet, and the rebound resilience is 76-85%.
Drawings
FIG. 1 is a photograph of a foamed material with a relief effect obtained in accordance with one embodiment of the present invention before foaming;
FIG. 2 is a photograph of a foamed material with a relief effect obtained in accordance with one embodiment of the present invention after foaming;
FIG. 3 is a photo of the foamed material with engraved effect obtained in example nine of the present invention before foaming;
FIG. 4 is a photograph of the foamed material with engraving effect obtained in the ninth embodiment of the present invention after foaming;
FIG. 5 is a SEM image of an antistatic foamed material obtained in example fifteen of the present invention;
FIG. 6 is a photograph showing a foamed material obtained in comparative example one;
FIG. 7 is a photograph showing a foamed material obtained in comparative example II;
FIG. 8 is a photograph of a foamed material obtained in comparative example three;
FIG. 9 is an SEM photograph of the foamed material obtained in comparative example IV.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method of a functional elastic foaming material, which comprises the following steps:
1) mixing raw materials including 60-100 parts by weight of thermoplastic polyester elastomer and 0-40 parts by weight of ethylene-vinyl acetate copolymer and/or thermoplastic polyurethane elastomer rubber to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), forming and crosslinking to obtain a plate;
3) and (3) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 2), wherein the saturation pressure is 16-30MPa, the saturation temperature is 80-120 ℃, the saturation time is 4-8h, the pressure relief time is 1-15s, and foaming is carried out for 5-30min at the temperature of 150 ℃ and 180 ℃ to obtain the functional elastic foaming material.
Preferably, the method further comprises, after the step 1) and before the step 2): adding an antistatic agent into the primary mixture, and continuously mixing to obtain a mixture; the addition amount of the antistatic agent is 5-12%.
Further, the antistatic agent is any one of graphene, carbon nanotubes, carbon fibers, conductive carbon black and metal fibers.
Again preferably, after the step 2) and before the step 3), further comprising: a) mixing chloroform, an organic solvent and an organic pigment according to a mass ratio of 8-12:20:1 to prepare a dye for later use; b) and (c) coating the dye obtained in the step a) on the plate obtained in the step 2) by using a brush or a pen.
Furthermore, the surface of the functional elastic foaming material is provided with a relief pattern, and the height of the relief pattern is 0.8-2.0 mm.
More preferably, the method further comprises, after the step 2) and before the step 3): A) mixing chloroform, an organic solvent and an organic pigment according to a mass ratio of 20-25:20:1 to prepare a dye for later use; B) and B), coating the dye obtained in the step A) on the plate obtained in the step 2) by using a brush or a pen.
Furthermore, the surface of the functional elastic foaming material is provided with a carved pattern, and the depth of the carved pattern is 1.0-2.5 mm.
Specifically, the mixing temperature is 180-185 ℃, and the mixing time is 3-10 min.
The functional elastic foaming material is prepared by the preparation method of the functional elastic foaming material.
The invention relates to application of a functional elastic foaming material, which is used as a midsole material.
Example one
The invention relates to a preparation method of a functional elastic foaming material with a relief effect, which comprises the following steps:
1) taking 100 parts by weight of thermoplastic polyester elastomer (TPEE) as a raw material, and mixing to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), molding, and then adopting 70kGy Co 60Performing electron beam irradiation crosslinking by using a radiation source to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and pigment carbon black according to a mass ratio of 10:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting two words of 'foaming' on the board obtained in the step 2) to obtain a board with Chinese characters;
5) placing the plate with the foaming character obtained in the step 4) into a reaction kettle for supercritical nitrogen intermittent heating foaming, wherein the saturation pressure is 16MPa, the saturation temperature is 120 ℃, the saturation time is 4h, and the pressure relief time is 1s, and taking out the plate to obtain the plate saturated with nitrogen; placing the plate saturated with nitrogen in an oven at 180 ℃, and foaming at constant temperature for 8min to obtain the functional elastic foaming material with the relief effect.
Example two
The invention relates to a preparation method of a functional elastic foaming material with a relief effect, which comprises the following steps:
1) taking raw materials, namely 90 parts by weight of thermoplastic polyester elastomer (TPEE) and 10 parts by weight of ethylene-vinyl acetate copolymer (EVA), and mixing to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), molding, and then adopting 60kGy Co 60Performing electron beam irradiation crosslinking by using a radiation source to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and pigment carbon black according to the mass ratio of 12:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting two words of 'wind and light' on the board obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 30MPa, the saturation temperature is 80 ℃, the saturation time is 8h, and the pressure relief time is 5s, so as to obtain a plate saturated with nitrogen; placing the obtained plate saturated with nitrogen in an oven at 180 ℃, and foaming at constant temperature for 5min to obtain the functional elastic foaming material with the relief effect.
EXAMPLE III
The invention relates to a preparation method of a functional elastic foaming material with a relief effect, which comprises the following steps:
1) taking raw materials, namely 80 parts by weight of thermoplastic polyester elastomer (TPEE) and 20 parts by weight of ethylene-vinyl acetate copolymer (EVA), and mixing to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), adding 0.65 part of vulcanizing agent BIPB, and then placing the mixture in a mold for crosslinking and molding to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and phthalocyanine blue according to a mass ratio of 10:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting two words of 'feeling and moving' on the plate obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 20MPa, the saturation temperature is 100 ℃, the saturation time is 4h, and the pressure relief time is 10s, so as to obtain a plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen at a constant temperature of 175 ℃ for 8min to obtain the functional elastic foaming material with the relief effect.
Example four
The invention relates to a preparation method of a functional elastic foaming material with a relief effect, which comprises the following steps:
1) taking raw materials, namely 70 parts by weight of thermoplastic polyester elastomer (TPEE) and 30 parts by weight of ethylene-vinyl acetate copolymer (EVA), and mixing to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), adding 0.65 part of vulcanizing agent BIPB, and then putting the mixture into a mould for cross-linking forming to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and aurora red according to the mass ratio of 10:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and coating English letters 'RELIEF' on the board obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 20MPa, the saturation temperature is 100 ℃, the saturation time is 4h, and the pressure relief time is 10s, so as to obtain a plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen at a constant temperature of 180 ℃ for 5min to obtain the functional elastic foaming material with the relief effect.
EXAMPLE five
The invention relates to a preparation method of a functional elastic foaming material with a relief effect, which comprises the following steps:
1) taking raw materials, mixing the raw materials, wherein the raw materials comprise 90 parts by weight of thermoplastic polyester elastomer (TPEE) and 10 parts by weight of thermoplastic polyurethane elastomer rubber (TPU), and obtaining a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), forming, and then irradiating and crosslinking by adopting a 50kGy electron beam to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and pigment carbon black according to the mass ratio of 8:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting two characters of 'national celebration' on the plate obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 25MPa, the saturation temperature is 100 ℃, the saturation time is 6 hours, and the pressure relief time is 10s, so as to obtain a plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen at a constant temperature of 165 ℃ for 15min to obtain the functional elastic foaming material with the relief effect.
EXAMPLE six
The invention relates to a preparation method of a functional elastic foaming material with a relief effect, which comprises the following steps:
1) mixing raw materials, wherein the raw materials comprise 80 parts by weight of thermoplastic polyester elastomer (TPEE) and 20 parts by weight of thermoplastic polyurethane elastomer rubber (TPU), and obtaining a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), forming, and then irradiating and crosslinking by adopting a 70kGy electron beam to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and carbon black according to a mass ratio of 10:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting two words of 'richness and strength' on the plate obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 20MPa, the saturation temperature is 115 ℃, the saturation time is 4h, and the pressure relief time is 8s, so as to obtain a plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen at a constant temperature of 180 ℃ for 5min to obtain the functional elastic foaming material with the relief effect.
EXAMPLE seven
The invention relates to a preparation method of a functional elastic foaming material with a relief effect, which comprises the following steps:
1) taking raw materials, mixing the raw materials, wherein the raw materials comprise 70 parts by weight of thermoplastic polyester elastomer (TPEE) and 30 parts by weight of thermoplastic polyurethane elastomer rubber (TPU), and obtaining a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), adding 0.7 part of vulcanizing agent BIPB, and vulcanizing and forming to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and carbon black according to a mass ratio of 10:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting two words of 'richness and strength' on the plate obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 20MPa, the saturation temperature is 115 ℃, the saturation time is 4h, and the pressure relief time is 6s, so as to obtain a plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen at a constant temperature of 170 ℃ for 12min to obtain the functional elastic foaming material with the relief effect.
Example eight
The invention relates to a preparation method of a functional elastic foaming material with a relief effect, which comprises the following steps:
1) mixing raw materials including 60 parts by weight of thermoplastic polyester elastomer (TPEE), 30 parts by weight of ethylene-vinyl acetate copolymer (EVA) and 10 parts by weight of thermoplastic polyurethane elastomer rubber (TPU) to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), adding 0.7 part of vulcanizing agent BIPB, and vulcanizing and forming to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and carbon black according to a mass ratio of 10:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting two characters of 'people' on the plate obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 20MPa, the saturation temperature is 100 ℃, the saturation time is 4h, and the pressure relief time is 6s, so as to obtain a plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen for 10min at the temperature of 170 ℃ to obtain the functional elastic foaming material with the relief effect.
Example nine
The invention relates to a preparation method of a functional elastic foaming material with a carving effect, which comprises the following steps:
1) taking 100 parts by weight of thermoplastic polyester elastomer (TPEE) as a raw material, and mixing to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), molding, and then adopting 70kGy Co 60Performing electron beam irradiation crosslinking by using a radiation source to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and an organic pigment according to a mass ratio of 20:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and writing two words of 'democratic' on the board obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 28MPa, the saturation temperature is 120 ℃, the saturation time is 6 hours, and the pressure relief time is 1s, so as to obtain a plate saturated with nitrogen; and (3) foaming the plate saturated with nitrogen at a constant temperature of 180 ℃ for 6min to obtain the functional elastic foaming material with the engraving effect.
Example ten
The invention relates to a preparation method of a functional elastic foaming material with a carving effect, which comprises the following steps:
1) taking raw materials, namely 90 parts by weight of thermoplastic polyester elastomer (TPEE) and 10 parts by weight of ethylene-vinyl acetate copolymer (EVA), and mixing to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), molding, and then adopting 70kGy Co 60Performing electron beam irradiation crosslinking by using a radiation source to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and an organic pigment according to a mass ratio of 25:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting 'carving' two characters on the board obtained in the step 2) to obtain a board with Chinese characters;
5) placing the plate with the carved character obtained in the step 4) into a reaction kettle for supercritical nitrogen intermittent heating foaming, wherein the saturation pressure is 30MPa, the saturation temperature is 80 ℃, the saturation time is 8h, the pressure release time is 15s, and taking out the plate to obtain a saturated plate with nitrogen; and (3) placing the plate saturated with nitrogen into an oven at 175 ℃, and foaming at constant temperature for 12min to obtain the functional elastic foaming material with the engraving effect.
EXAMPLE eleven
The invention relates to a preparation method of a functional elastic foaming material with a carving effect, which comprises the following steps:
1) taking raw materials, namely 70 parts by weight of thermoplastic polyester elastomer (TPEE) and 30 parts by weight of ethylene-vinyl acetate copolymer (EVA), and mixing to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), adding 0.65 part of vulcanizing agent BIPB, and then putting the mixture into a mould for cross-linking forming to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and aurora red pigment according to the mass ratio of 20:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting 'grinding' Chinese characters on the board obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 25MPa, the saturation temperature is 100 ℃, the saturation time is 5 hours, and the pressure relief time is 10s, so as to obtain a plate saturated with nitrogen; and (3) foaming the plate saturated with nitrogen at a constant temperature of 180 ℃ for 6min to obtain the functional elastic foaming material with the engraving effect.
Example twelve
The invention relates to a preparation method of a functional elastic foaming material with a carving effect, which comprises the following steps:
1) taking raw materials, mixing the raw materials, wherein the raw materials comprise 90 parts by weight of thermoplastic polyester elastomer (TPEE) and 10 parts by weight of thermoplastic polyurethane elastomer rubber (TPU), and obtaining a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), forming, and then irradiating and crosslinking by adopting a 50kGy electron beam to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and pigment carbon black according to the mass ratio of 22:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting two words of 'richness and strength' on the plate obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 20MPa, the saturation temperature is 100 ℃, the saturation time is 6h, and the pressure relief time is 10s, so as to obtain a plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen at a constant temperature of 170 ℃ for 10min to obtain the functional elastic foaming material with the engraving effect.
EXAMPLE thirteen
The invention relates to a preparation method of a functional elastic foaming insole with a carving effect, which comprises the following steps:
1) mixing raw materials including 75 parts by weight of thermoplastic polyester elastomer (TPEE), 15 parts by weight of ethylene-vinyl acetate copolymer (EVA) and 10 parts by weight of thermoplastic polyurethane elastomer rubber (TPU) to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), then performing injection molding to obtain a shoe type blank, and performing irradiation crosslinking on the shoe type blank in a 70kGy electron beam irradiation atmosphere to obtain a crosslinked shoe insole blank;
3) mixing chloroform, absolute ethyl alcohol and pigment carbon black according to a mass ratio of 20:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and writing a 'BLACK' English letter on the side surface of the cross-linked insole blank obtained in the step 2), which is close to the heel; writing a 'BLUE' English letter on the side surface of the insole blank close to the half sole of the shoe by using a commercially available BLUE marking pen;
5) carrying out supercritical nitrogen intermittent heating foaming on the insole blank written with the letters obtained in the step 4), wherein the saturation pressure is 25MPa, the saturation temperature is 115 ℃, the saturation time is 10 hours, the pressure relief time is 6s, and taking out the saturated insole blank with nitrogen, wherein the insole blank is not foamed and has no change in shape;
6) placing the shoe blank saturated with nitrogen obtained in the step 5) at 180 ℃, and foaming at constant temperature for 15min to obtain the functional elastic foamed shoe insole with the engraved effect on the side surface of the heel.
Example fourteen
The invention relates to a preparation method of a functional elastic foaming material with a carving effect, which comprises the following steps:
1) mixing raw materials including 60 parts by weight of thermoplastic polyester elastomer (TPEE), 10 parts by weight of ethylene-vinyl acetate copolymer (EVA) and 30 parts by weight of thermoplastic polyurethane elastomer rubber (TPU) to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), adding 0.65 part of vulcanizing agent BIPB, and vulcanizing and forming to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and pigment carbon black according to a mass ratio of 20:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and painting two words of 'richness and strength' on the plate obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 25MPa, the saturation temperature is 115 ℃, the saturation time is 5 hours, and the pressure relief time is 6s, so as to obtain a plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen for 18min at the temperature of 170 ℃ to obtain the functional elastic foaming material with the engraving effect.
Example fifteen
The invention relates to a preparation method of an antistatic functional elastic foaming material, which comprises the following steps:
1) taking 100 parts by weight of thermoplastic polyester elastomer (TPEE) as a raw material, and mixing in an internal mixer to obtain a primary mixture for later use;
2) adding an antistatic agent graphene into the primary mixture, and continuously mixing to obtain a mixture, wherein the addition amount of the antistatic agent is 10%;
3) mixing the mixture obtained in the step 2), wherein the mixing temperature is 180 ℃, the mixing time is 10min, forming, and placing in an electron beam irradiation atmosphere of 70kGy for irradiation crosslinking to obtain a plate;
4) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 3), wherein the saturation pressure is 16MPa, the saturation temperature is 120 ℃, the saturation time is 4h, and the pressure relief time is 1s, so as to obtain a plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen for 30min at 150 ℃ to obtain the functional elastic foaming material.
Example sixteen
The invention relates to a preparation method of an antistatic functional elastic foaming material, which comprises the following steps:
1) taking raw materials, namely 80 parts by weight of thermoplastic polyester elastomer (TPEE) and 20 parts by weight of thermoplastic polyurethane elastomer rubber (TPU), placing the raw materials in an internal mixer, and mixing to obtain a primary mixture for later use;
2) adding an antistatic agent-metal fiber into the primary mixture, and continuously mixing to obtain a mixture, wherein the addition amount of the antistatic agent is 6%;
3) mixing the mixture obtained in the step 2), wherein the mixing temperature is 185 ℃, the mixing time is 3min, adding 0.65 part of vulcanizing agent BIPB, and vulcanizing and forming to obtain a plate;
4) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 3), wherein the saturation pressure is 20MPa, the saturation temperature is 100 ℃, the saturation time is 8h, and then, rapidly decompressing at the decompression speed of 30MPa/S to obtain the plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen at a constant temperature of 175 ℃ for 10min to obtain the functional elastic foaming material.
Example seventeen
The invention relates to a preparation method of an antistatic functional elastic foaming material, which comprises the following steps:
1) taking raw materials, namely 90 parts by weight of thermoplastic polyester elastomer (TPEE) and 10 parts by weight of ethylene-vinyl acetate copolymer (EVA), placing the raw materials in an internal mixer, and mixing to obtain a primary mixture for later use;
2) adding an antistatic agent, namely Carbon Nano Tubes (CNT), into the primary mixture, and continuously mixing to obtain a mixture, wherein the addition amount of the antistatic agent is 7%;
3) mixing the mixture obtained in the step 2), wherein the mixing temperature is 120 ℃, the mixing time is 7min, adding 0.65 part of vulcanizing agent BIPB, and vulcanizing and forming to obtain a plate;
4) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 3), wherein the saturation pressure is 30MPa, the saturation temperature is 80 ℃, the saturation time is 8h, and then, rapidly decompressing at the decompression speed of 30MPa/S to obtain the plate saturated with nitrogen; and foaming the obtained plate saturated with nitrogen for 12min at 180 ℃ to obtain the functional elastic foaming material.
EXAMPLE eighteen
The invention relates to a preparation method of an antistatic functional elastic foaming material, which comprises the following steps:
1) taking raw materials, namely 60 parts by weight of thermoplastic polyester elastomer (TPEE), 30 parts by weight of ethylene-vinyl acetate copolymer (EVA) and 10 parts by weight of thermoplastic polyurethane elastomer rubber (TPU), placing the raw materials in an internal mixer, and mixing to obtain a primary mixture for later use;
2) adding an antistatic agent, namely conductive carbon black, into the primary mixture, and continuously mixing to obtain a mixture, wherein the addition amount of the antistatic agent is 12%;
3) mixing the mixture obtained in the step 2), wherein the mixing temperature is 180 ℃, the mixing time is 10min, adding 0.5 part of vulcanizing agent BIPB, and vulcanizing and forming to obtain a plate;
4) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 3), wherein the saturation pressure is 24MPa, the saturation temperature is 110 ℃, the saturation time is 6h, and then, rapidly decompressing at the decompression speed of 30MPa/S to obtain the plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen at the constant temperature of 170 ℃ for 8min to obtain the functional elastic foaming material.
Comparative example 1
A preparation method of a foaming material comprises the following steps:
1) taking 100 parts by weight of ethylene-vinyl acetate copolymer (EVA) and 0.65 part by weight of vulcanizing agent BIPB as raw materials, mixing the BIPB into the EVA in an internal mixer at 100 ℃, and then preparing an EVA plate under the conditions that the temperature is 110 ℃ and the pressure is 10 MPa;
2) mixing chloroform, absolute ethyl alcohol and pigment carbon black according to a mass ratio of 10:20:1 to prepare a dye for later use;
3) dipping the dye obtained in the step 2) by using a brush, and painting the plate obtained in the step 1) with 'sample' characters;
4) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 3), wherein the saturation pressure is 20MPa, the saturation temperature is 80 ℃, the saturation time is 4h, and then, carrying out pressure relief at the speed of 30MPa/S to obtain a plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen for 5min at constant temperature in an oven at the temperature of 150 ℃ to obtain the foaming material.
Comparative example No. two
A preparation method of a foaming material comprises the following steps:
1) taking raw materials, namely 100 parts by weight of thermoplastic polyurethane elastomer rubber (TPU) and 0.65 part by weight of vulcanizing agent BIPB, mixing the BIPB into the TPU in an internal mixer at 130 ℃, and then preparing a TPU plate under the conditions that the temperature is 180 ℃ and the pressure is 10 MPa;
2) mixing chloroform, absolute ethyl alcohol and pigment carbon black according to a mass ratio of 10:20:1 to prepare a dye for later use;
3) dipping the dye obtained in the step 2) by using a brush, and painting a T letter on the plate obtained in the step 1);
4) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 3), wherein the saturation pressure is 20MPa, the saturation temperature is 130 ℃, the saturation time is 4h, and then, carrying out pressure relief at the speed of 30MPa/S to obtain a plate saturated with nitrogen; and (3) foaming the obtained board saturated with nitrogen for 6min at constant temperature in an oven at 165 ℃ to obtain the foam material.
Comparative example No. three
A preparation method of a foaming material comprises the following steps:
1) taking raw materials, namely 50 parts by weight of thermoplastic polyester elastomer (TPEE), 30 parts by weight of ethylene-vinyl acetate copolymer (EVA) and 20 parts by weight of thermoplastic polyurethane elastomer rubber (TPU), and mixing to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), adding 0.65 part of vulcanizing agent BIPB, and vulcanizing and forming to obtain a plate;
3) mixing chloroform, absolute ethyl alcohol and an organic pigment according to a mass ratio of 10:20:1 to prepare a dye for later use;
4) dipping the dye obtained in the step 3) by using a brush, and coating and writing two words of 'floating carving' on the plate obtained in the step 2);
5) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 4), wherein the saturation pressure is 20MPa, the saturation temperature is 100 ℃, the saturation time is 4h, and the pressure relief time is 6s, so as to obtain a plate saturated with nitrogen; and foaming the obtained plate saturated with nitrogen for 6min at 180 ℃ to obtain the foam material.
Comparative example No. four
A preparation method of a foaming material comprises the following steps:
1) taking raw materials, namely 50 parts by weight of thermoplastic polyester elastomer, 20 parts by weight of ethylene-vinyl acetate copolymer (EVA) and 30 parts by weight of thermoplastic polyurethane elastomer rubber (TPU), placing the raw materials in an internal mixer, and mixing to obtain a primary mixture for later use;
2) adding an antistatic agent, namely conductive carbon black, into the primary mixture, and continuously mixing to obtain a mixture, wherein the addition amount of the antistatic agent is 10%;
3) mixing the mixture obtained in the step 2), wherein the mixing temperature is 180 ℃, the mixing time is 10min, adding 0.65 part of vulcanizing agent BIPB, and vulcanizing and forming to obtain a plate;
4) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 3), wherein the saturation pressure is 24MPa, the saturation temperature is 110 ℃, the saturation time is 6h, and then, rapidly decompressing at the decompression speed of 30MPa/S to obtain the plate saturated with nitrogen; and (3) foaming the obtained plate saturated with nitrogen at a constant temperature of 170 ℃ for 8min to obtain the foam material.
The density, the rebound resilience and the surface relief effect of the foamed sheet with the relief effect obtained in the first to the eighth examples are respectively measured, wherein the density is measured according to a GB/T6344-1995 drainage method, the rebound resilience is measured according to a GB/T6670-2008 method, the ball rebound resilience of the foamed sheet is measured, the surface relief effect is observed by naked eyes, the surface relief condition is objectively recorded, and the experimental results are listed in Table 1.
The density, the rebound resilience and the surface engraving effect of the foamed sheet with the engraving effect obtained in the ninth embodiment to the fourteenth embodiment are respectively measured, wherein the density is measured according to a GB/T6344-1995 drainage method, the rebound resilience is measured according to a method specified in GB/T6670-2008, the ball falling rebound resilience of the foamed sheet is measured according to the surface engraving effect by adopting a visual observation method, the surface engraving condition is objectively recorded, and the experimental results are listed in Table 2.
The antistatic foamed sheets obtained in the fifteen to eighteen examples were measured for surface resistance, rebound resilience and compression set, respectively, wherein the surface resistance of the foamed sheet was measured according to the method specified in GB/T11210-1989, the rebound resilience was measured according to the method specified in GB/T6670-2008, the ball rebound resilience of the foamed sheet was measured according to the method specified in GB/T6669-2008, and the results of the test were shown in Table 3.
And (3) respectively measuring the density, the rebound resilience and the surface effect of the foamed plates obtained in the first to fourth comparative examples, wherein the density is measured according to a GB/T6344-1995 drainage method, the rebound resilience is measured according to a GB/T6670-2008 specified method, the ball rebound resilience of the foamed plates is measured according to a visual observation method, the surface effect is objectively recorded, and the experimental results are listed in Table 3.
TABLE 1 Experimental results of the performance test of the foam material with surface relief effect
Figure BDA0002244842600000191
As can be seen from tables 1 and 4, the foamed material obtained by the method of the present invention has a significant surface with protrusions having a letter pattern, and the height of the protrusions is 0.8 to 1.5mm, strong stereoscopic impression and obvious relief effect; however, the foamed materials of comparative examples one to four were all surface-smooth without any pattern. As can be seen from the attached figures 1, 2, 6, 7 and 8, the foamed material obtained by the method of the present invention has a significant surface relief effect. Secondly, the density of the foaming material obtained by the method of the invention is 0.10-0.13g/cm 3This is much less than the density of the foamed materials of comparative examples one to four, and the weight is light. In addition, the resilience of the foaming material obtained by the method is 78-85%, which is far greater than that of the foaming materials of comparative examples I-IV, and the foaming material has good resilience.
Table 2 foam material performance test experimental results with surface engraving effect
Figure BDA0002244842600000201
As can be seen from tables 2 and 4, the foam material obtained by the method of the invention has obvious character pattern depression on the surface, the depth of the character pattern depression is 1.0-2.5mm, the stereoscopic impression is strong, and the obvious engraving effect is achieved; however, the foamed materials of comparative examples one to four were all surface-smooth without any pattern. As can be seen from the attached figures 3, 4, 6, 7 and 8, the surface engraving effect of the foamed material obtained by the method of the invention is obvious. Secondly, the density of the foaming material obtained by the method of the invention is 0.10-0.13g/cm 3This is much less than the density of the foamed materials of comparative examples one to four, and the weight is very light. In addition, the resilience of the foaming material obtained by the method is 78-85%, which is far greater than that of the foaming materials of comparative examples I-IV, and the foaming material has good resilience.
TABLE 3 Experimental results of testing the properties of antistatic foaming materials
Sample name Surface resistance (omega) Rebound resilience (%) Compression set (%) Density (g/cm) 3)
Example fifteen 9.363×10 6 81 16 0.15
Example sixteen 1.637×10 8 83 18 0.14
Example seventeen 7.728×10 8 78 15 0.17
EXAMPLE eighteen 8.735×10 6 76 14 0.18
As can be seen from tables 3 and 4, the present inventionThe surface resistance of the foamed material obtained by the method of the invention is 8.735 multiplied by 10 6-7.728×10 8Omega, which is much less than the surface resistance of the foamed materials of comparative examples one to four, has a significant antistatic effect. Secondly, the rebound resilience of the foaming material obtained by the method is between 76 and 83 percent, which is far greater than that of the foaming materials of comparative examples I to IV, and the foaming material has good rebound resilience. In addition, the compression set of the foaming material obtained by the method of the invention is between 14 and 18 percent, which is far less than that of the foaming materials of comparative examples I to IV, and the foaming material has obvious compression resistance and recovery capability. As can be seen from the attached FIGS. 5 and 9, the average pore diameter of the cells of the foamed material obtained by the method of the present invention is 90 μm, the pore diameter of the cells is large and uniform, and the cell walls are thin and are arranged closely; the average pore diameter of the cells of the foamed material obtained in the comparative example four is only 50 microns, the pore diameter of the cells is small, the walls of the cells are thick, the cells are not tightly arranged, and the density is high.
TABLE 4 test results of the foam Material Properties
Sample name Density (g/cm) 3) Rebound resilience (%) Surface resistance (omega) Compression set (%) Surface effects
Comparative example 1 0.14 50 4.8×10 12 34 Is free of
Comparative example No. two 0.16 59 4.9×10 12 43 Is free of
Comparative example No. three 0.13 50 4.6×10 12 35 Is free of
Comparative example No. four 0.32 38 1.0×10 12 23 Is free of
Therefore, compared with the prior art, the invention has the beneficial effects that: the invention takes the thermoplastic polyester elastomer or the mixture of the thermoplastic polyester elastomer and any one or two of ethylene-vinyl acetate copolymer and thermoplastic polyurethane elastomer rubber as the raw material, adopts the supercritical nitrogen intermittent heating foaming method to directly react in one step to obtain the lightweight high-elastic plate, the product size is not limited in the production process of the high-elastic plate, the equipment is simple, no chemical foaming agent is used, the process is simple and environment-friendly, the operation is convenient, and the production is carried outThe efficiency is high, and the production cost is low; the density of the obtained product is 0.08-0.18g/cm 3The shoe sole has the advantages of light weight, ultrahigh rebound resilience, wide application range, particular suitability for shoe insole materials, comfortable wearing of the obtained shoe, light and soft texture, good rebound resilience and good protection effect on feet, and the rebound resilience is 76-85%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A preparation method of a functional elastic foaming material is characterized by comprising the following steps:
1) mixing raw materials including 60-100 parts by weight of thermoplastic polyester elastomer and 0-40 parts by weight of ethylene-vinyl acetate copolymer and/or thermoplastic polyurethane elastomer rubber to obtain a primary mixture for later use;
2) mixing the primary mixture obtained in the step 1), and forming and crosslinking to obtain a plate;
3) and (3) carrying out supercritical nitrogen intermittent heating foaming on the plate obtained in the step 2), wherein the saturation pressure is 16-30MPa, the saturation temperature is 80-120 ℃, the saturation time is 4-8h, the pressure relief time is 1-15s, and foaming is carried out for 5-30min at the temperature of 150 ℃ and 180 ℃ to obtain the functional elastic foaming material.
2. The method for preparing a functional elastic foamed material according to claim 1, characterized in that:
after the step 1) and before the step 2), further comprising: adding an antistatic agent into the primary mixture, and continuously mixing to obtain a mixture; the addition amount of the antistatic agent is 5-12%.
3. The method for preparing a functional elastic foamed material according to claim 2, characterized in that:
the antistatic agent is any one of graphene, carbon nano tubes, carbon fibers, conductive carbon black and metal fibers.
4. The method for preparing functional elastic foaming material according to claim 1, further comprising after the step 2) and before the step 3):
a) mixing chloroform, an organic solvent and an organic pigment according to a mass ratio of 8-12:20:1 to prepare a dye for later use;
b) and (c) coating the dye obtained in the step a) on the plate obtained in the step 2) by using a brush or a pen.
5. The method for preparing functional elastic foamed material according to claim 4, characterized in that:
the surface of the functional elastic foaming material is provided with a relief pattern, and the height of the relief pattern is 0.8-2.0 mm.
6. The method for preparing functional elastic foaming material according to claim 1, further comprising after the step 2) and before the step 3):
A) mixing chloroform, an organic solvent and an organic pigment according to a mass ratio of 20-25:20:1 to prepare a dye for later use;
B) and B), coating the dye obtained in the step A) on the plate obtained in the step 2) by using a brush or a pen.
7. The method for preparing a functional elastic foam material according to claim 6, wherein:
the surface of the functional elastic foaming material is provided with engraved patterns, and the depth of the engraved patterns is 1.0-2.5 mm.
8. The method for preparing functional elastic foamed material according to any one of claims 1 to 7, characterized in that:
the mixing temperature is 180 ℃ and 185 ℃, and the mixing time is 3-10 min.
9. A functional elastic foam material characterized by:
the functional elastic foam material is prepared by the method for preparing the functional elastic foam material according to any one of claims 1 to 8.
10. Use of a functional elastic foam material according to claim 9, characterized in that:
the functional elastic foaming material is used as a midsole material.
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CN114083740A (en) * 2021-11-19 2022-02-25 苏州申赛新材料有限公司 Method for preparing bicolor foamed sheet based on space limitation

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