CN115044189A - Polymer foam product with hierarchical pore structure and preparation method thereof - Google Patents
Polymer foam product with hierarchical pore structure and preparation method thereof Download PDFInfo
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- 239000006260 foam Substances 0.000 title claims abstract description 146
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000002149 hierarchical pore Substances 0.000 title description 4
- 210000004027 cell Anatomy 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 28
- 210000003850 cellular structure Anatomy 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims description 39
- 239000011324 bead Substances 0.000 claims description 30
- 238000005245 sintering Methods 0.000 claims description 27
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 24
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 23
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 23
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000000806 elastomer Substances 0.000 claims description 5
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- -1 polybutylene adipate terephthalate Polymers 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 229920006285 olefinic elastomer Polymers 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 18
- 238000005299 abrasion Methods 0.000 abstract description 4
- 230000003373 anti-fouling effect Effects 0.000 abstract description 2
- 229920002614 Polyether block amide Polymers 0.000 description 11
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 description 11
- 230000006835 compression Effects 0.000 description 10
- 238000007906 compression Methods 0.000 description 10
- 238000013459 approach Methods 0.000 description 5
- 238000009768 microwave sintering Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
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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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
- C08J9/232—Forming foamed products by sintering expandable particles
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The present invention provides a polymeric foam article having a hierarchical cell structure and a method of making the same. The outer surface of the polymeric foam article has a layer of dense, unfoamed skin structure that constitutes the primary cell structure of the polymeric foam article; a second-stage cellular structure is arranged inside the skin layer structure; a third level of cell structure is present within the second level of cell structure. Compared with the polymer foam product prepared by the conventional process, the polymer foam product prepared by the invention has higher tearing strength and resilience, more excellent appearance quality, and more resistance to external force impact and abrasion, and the dense, smooth and flat skin layer can also endow the polymer foam product with more excellent anti-fouling capability.
Description
Technical Field
The invention belongs to the technical field of forming processes, and particularly relates to a polymer foam product with a hierarchical pore structure and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Thermoplastic elastomer foam is an important class of polymer foam material, and is an ideal material for manufacturing midsoles of sports shoes due to excellent rebound characteristics. Currently, the middle soles of sports shoes adopting thermoplastic elastomer foam are mainly processed and manufactured by two process approaches, wherein one process approach is to foam and make blanks firstly and then mould pressing and forming, and the other process approach is to foam and make foam beads firstly and then sinter and form. The first approach produces a thermoplastic elastomer foam midsole with excellent appearance quality, but has poor rebound and tear strength due to a single cell structure; the second approach is to prepare a midsole with higher rebound resilience and tear strength, but the product has an insufficiently fine appearance, a strong granular feel, and is not resistant to external impact and abrasion, and the surface is easily damaged.
Disclosure of Invention
In order to solve the problems of poor tearing strength, low rebound resilience, poor appearance quality and the like of a thermoplastic elastomer foam product prepared by a conventional foaming molding process, the invention provides a polymer foam product with a hierarchical pore structure and a preparation method thereof. The thermoplastic elastomer foam product prepared by the invention has a compact skin layer structure and a three-level cell structure, can endow the foam product with more excellent tearing strength and rebound resilience, and can also obviously improve the appearance quality of the foam product, and the compact flat layer can also improve the impact resistance of the foam product and reduce the surface damage phenomenon in the using process.
In order to achieve the above object, the present invention provides the following technical solutions.
In a first aspect of the present invention, a polymeric foam article having a hierarchical cell structure is provided. The outer surface of the polymeric foam article has a layer of dense, unfoamed skin structure that constitutes the primary cell structure of the polymeric foam article; a second-level cell structure exists inside the skin layer structure, and the inside of the skin layer structure consists of the second-level cell structure; a third-stage cellular structure exists inside the second-stage cellular structure, the inside of the second-stage cellular structure is composed of the third-stage cellular structure, and the thickness of the skin layer structure ranges from 2 micrometers to 500 micrometers; the equivalent sphere diameter range of the second-stage cellular structure is 0.5 mm-10 mm, and the wall thickness range is 0.5 μm-50 μm; the equivalent spherical diameter range of the third-stage cellular structure is 5-500 mu m.
Preferably, the thickness of the skin structure ranges from 10 μm to 100 μm.
Preferably, the equivalent spherical diameter of the second-stage cellular structure ranges from 2mm to 8mm, and the wall thickness ranges from 5 μm to 30 μm.
Preferably, the equivalent spherical diameter of the third-stage cells ranges from 20 μm to 200 μm.
This closely knit cortex structure has smooth exquisite outward appearance, has very high intensity simultaneously, can play fine guard action to inside cell structure, is showing external force impact strength and the abrasion strength of nai who improves foam product, promotes foam product's whole outward appearance quality simultaneously, reinforcing surface anti-soil ability. The cells of the second stage of cells are effective to enhance the tear strength of the polymeric foam article and to increase the resiliency of the polymeric foam article. The third-stage foam holes and the second-stage foam holes are matched with each other, so that the polymer foam product is light and high in resilience, and meanwhile, the third-stage foam holes are smallest in size, so that the scattering capacity of the polymer foam product to natural light can be enhanced, and the polymer foam product is endowed with more beautiful color.
In a second aspect of the present invention, there is provided a method for preparing a polymer foam having a dense skin layer and a hierarchical cell structure, comprising the steps of:
(1) sintering and molding the thermoplastic elastomer bead foam at one time to obtain a prefabricated blank with a certain shape and structure;
(2) and (3) placing the prefabricated blank into a mould for secondary sintering molding, rapidly heating the mould, closing the mould to press the prefabricated blank, and rapidly cooling the mould after press molding so as to cool and shape the polymer foam product in the mould.
Further, the thermoplastic elastomer is one or more of Thermoplastic Polyurethane (TPU), thermoplastic polyester elastomer (TPEE), thermoplastic nylon elastomer (PEBA), olefin elastomer (TPO, TPV or POE), polybutylene adipate terephthalate (PBAT) or a mixture thereof.
Further, the thermoplastic elastomer bead foam has an equivalent spherical diameter in the range of 0.5mm to 10mm, more preferably in the range of 2mm to 8mm, and the bead foam has a density of 0.05g/cm 3 ～0.18g/cm 3 Further, it is preferable that the density is in the range of 0.08g/cm 3 ～0.15g/cm 3 。
Further, the primary sintering molding can be steam heating molding or microwave heating molding, and the temperature range of the primary sintering molding is 100-160 ℃, and the more preferable sintering temperature range is 110-140 ℃.
Further, the secondary sintering molding rapidly heats the mold to 110-180 ℃, and the more preferable temperature range of the mold is 120-160 ℃.
The effect of the post-sintering molding is to give the polymer foam preform prepared in the first step a dense skin structure and a precise shape appearance structure.
Compared with the prior art, the invention has the following obvious advantages:
compared with the polymer foam product prepared by the conventional process, the polymer foam product prepared by the invention has higher tearing strength and resilience, more excellent appearance quality, and more resistance to external force impact and abrasion, and the dense, smooth and flat skin layer can also endow the polymer foam product with more excellent anti-fouling capability.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic representation of a polymeric foam article having a hierarchical cell structure.
FIG. 2 is a process flow for the manufacture of a polymeric foam article having a solid skin and a hierarchical cell structure.
Fig. 3 is a process flow of the processing of the midsole of the sports shoe.
Fig. 4 is a cross-sectional view of the midsole of the sports shoe.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The present invention relates to a polymeric foam article having a dense skin layer and a hierarchical cell structure. As shown in FIG. 1, the outer surface of the polymer foam article has a dense, unfoamed skin structure that also constitutes the primary cell structure of the polymer foam article, with a secondary cell structure within the dense skin and a tertiary cell structure within the secondary cells.
Wherein, cortex structure thickness scope is 2 mu m ~ 500 mu m, and further preferred scope is 10 mu m ~ 100 mu m, and this compact cortex structure has smooth exquisite outward appearance, has very high intensity simultaneously, can play fine guard action to inside cell structure, is showing the external force impact strength and the wearing and tearing intensity that improve foam product, promotes foam product's whole outward appearance quality simultaneously, strengthens surface anti-soil ability. The equivalent spherical diameter of the second-stage foam holes ranges from 0.5mm to 10mm, the more preferable equivalent spherical diameter ranges from 2mm to 8mm, the wall thickness of the second-stage foam holes ranges from 0.5 mu m to 50 mu m, the more preferable range is from 5 mu m to 30 mu m, and the second-stage foam holes can effectively enhance the tear strength of the polymer foam product and improve the resilience performance of the polymer foam product. The equivalent spherical diameter range of the third-stage foam holes is 5-500 mu m, the more preferable equivalent spherical diameter range is 20-200 mu m, the third-stage foam holes and the second-stage foam holes are matched with each other, so that the polymer foam product can be endowed with the characteristics of light weight and high resilience, and meanwhile, the third-stage foam holes are smallest in size, so that the scattering capacity of the polymer foam product on natural light can be enhanced, and the polymer foam product is endowed with more beautiful color.
The process for preparing a polymer foam having a dense skin layer and a hierarchical cell structure comprises two process steps, as shown in fig. 2. The first process step is one-step sintering molding, the molding step is to sinter a thermoplastic elastomer bead foam into a preform with a certain shape and structure, the thermoplastic elastomer is one or a mixture of more of Thermoplastic Polyurethane (TPU), thermoplastic polyester elastomer (TPEE), thermoplastic nylon elastomer (PEBA), olefin elastomer (TPO, TPV or POE) and polybutylene adipate terephthalate (PBAT), the equivalent spherical diameter of the bead foam is 0.5 mm-10 mm, the more preferable equivalent spherical diameter is 2 mm-8 mm, and the density of the bead foam is 0.05g/cm 3 ～0.18g/cm 3 Further, the preferable density range is 0.08g/cm 3 ～0.15g/cm 3 The primary sintering molding can be steam heating molding or microwave heating molding, the temperature range of the primary sintering molding is 100-160 ℃, and the more preferable sintering temperature range is 110-140 ℃. The second process step is a secondary sintering molding, which is used for endowing the polymer foam prefabricated blank prepared in the first step with a compact skin structure and a precise shape appearance structure, and the secondary sintering molding is performedWhen in use, the polymer prefabricated blank prepared in the first step is placed in a mould, the temperature of the mould is rapidly heated to 110-180 ℃, the further preferable temperature range of the mould is 120-160 ℃, then the mould is closed to press the polymer foam prefabricated blank, after the pressing and forming, the mould is rapidly cooled to cool and shape the polymer foam product in the mould, finally, the mould is opened, and the finally formed polymer foam product is taken out.
Embodiment 1
Fig. 3 shows a processing flow of the first embodiment. The polymer foam beads employed in this example were aliphatic TPU bead foam having a true density of 0.08g/cm 3 The bead foam has an equivalent spherical diameter of 4mm and is formed by the following process steps:
in the first step, TPU bead foam is sintered into a TPU foam prefabricated blank by adopting a steam molding forming process, the sintering temperature is 130 ℃, and the density of the TPU foam prefabricated blank is 0.09g/cm 3 。
And secondly, putting the TPU foam prefabricated blank prepared in the first step into a hot molding die, quickly heating the die to 150 ℃, closing the die to press the TPU foam prefabricated blank, quickly cooling the die and the TPU foam product in the die after pressing is finished, and finally opening the die and taking out the compression-molded TPU foam product.
The density of the final compression molded TPU foam article was measured to be 0.13g/cm 3 The thickness of the compact skin layer of the foam product is 30 μm, the equivalent spherical diameter of the second-stage cells is 3.7mm, the wall thickness of the second-stage cells is 10 μm, and the equivalent spherical diameter of the third-stage cells is 120 μm; the foam product had a ball rebound coefficient of 72%, a tensile strength of 3.5MPa, an elongation at break of 350%, and a tear strength of 2.2kg/cm 2 And a permanent compression set of 25%. Fig. 4 shows a schematic cross-sectional structure of the finally-prepared midsole.
Example II
The polymer foam beads employed in this example were TPEE bead foam having a true density of 0.08g/cm 3 The bead foam has an equivalent spherical diameter of 2.4mm and is formed by the following process:
in the first step, the first step is that,adopting a microwave sintering molding process to sinter the TPEE bead foam into a TPEE foam prefabricated blank, wherein the sintering temperature is 140 ℃, and the density of the TPEE foam prefabricated blank is 0.08g/cm 3 。
And secondly, placing the TPEE foam prefabricated blank prepared in the first step into a hot molding die, quickly heating the die to 160 ℃, closing the die to press the TPEE foam prefabricated blank, quickly cooling the die and the TPEE foam product in the die after pressing is finished, and finally opening the die and taking out the TPEE foam product formed by pressing.
The density of the final compression molded TPEE foam article was measured to be 0.12g/cm 3 The thickness of the compact skin layer of the foam product is 10 microns, the equivalent spherical diameter of the second-stage cells is 2mm, the wall thickness of the second-stage cells is 10 microns, and the equivalent spherical diameter of the third-stage cells is 20 microns; the foam product had a ball rebound coefficient of 70%, a tensile strength of 3.8MPa, an elongation at break of 300%, and a tear strength of 2.6kg/cm 2 And a permanent compression set of 27%.
Example three
The polymer foam beads employed in this example were PEBA bead foam having a true density of 0.13g/cm 3 The equivalent spherical diameter of the bead foam is 8mm, and the molding process comprises the following steps:
firstly, sintering the PEBA bead foam into a PEBA foam prefabricated blank by adopting a microwave sintering molding process, wherein the sintering temperature is 140 ℃, and the density of the PEBA foam prefabricated blank is 0.14g/cm 3 。
And secondly, putting the PEBA foam prefabricated blank prepared in the first step into a hot-molding die, quickly heating the die to 140 ℃, closing the die to press the PEBA foam prefabricated blank, quickly cooling the die and the PEBA foam product in the die after pressing is finished, and finally opening the die and taking out the press-molded PEBA foam product.
The density of the final compression molded PEBA foam article was measured to be 0.16g/cm 3 The thickness of the compact skin layer of the foam product is 40 μm, the equivalent spherical diameter of the second-stage cells is 7mm, the wall thickness of the second-stage cells is 25 μm, and the equivalent spherical diameter of the third-stage cells is 75 μm; the foam article has a ball rebound coefficient of75%, tensile strength of 2.6MPa, elongation at break of 280%, and tear strength of 1.8kg/cm 2 And a permanent compression set of 22%.
Example four
The polymer foam beads employed in this example were polyester TPU bead foam having a true density of 0.15g/cm 3 The bead foam has an equivalent spherical diameter of 10mm and is formed by the following process:
firstly, sintering TPU bead foam into a TPU foam prefabricated blank by adopting a microwave sintering molding process, wherein the sintering temperature is 150 ℃, and the density of the TPU foam prefabricated blank is 0.16g/cm 3 。
And secondly, putting the TPU foam prefabricated blank prepared in the first step into a hot molding die, quickly heating the die to 160 ℃, closing the die to press the TPU foam prefabricated blank, quickly cooling the die and the TPU foam product in the die after pressing is finished, and finally opening the die and taking out the compression-molded TPU foam product.
The density of the final compression molded TPU foam article was measured to be 0.18g/cm 3 The thickness of the compact skin layer of the foam product is 100 μm, the equivalent spherical diameter of the second-stage cells is 8mm, the wall thickness of the second-stage cells is 30 μm, and the equivalent spherical diameter of the third-stage cells is 200 μm; the foam product has a ball rebound coefficient of 65%, a tensile strength of 3.8MPa, an elongation at break of 360%, and a tear strength of 2.8kg/cm 2 And a permanent compression set of 28%.
Example five
The polymer foam beads used in this example were olefinic thermoplastic elastomer (TPO) bead foam having a true density of 0.09g/cm 3 The bead foam has an equivalent spherical diameter of 2mm and is formed by the following process steps:
firstly, adopting a microwave sintering molding process to sinter TPO bead foam into a TPO foam preform, wherein the sintering temperature is 125 ℃, and the density of the TPO foam preform is 0.11g/cm 3 。
And step two, putting the TPO foam preform prepared in the step one into a hot-molding die, rapidly heating the die to 135 ℃, closing the die to press the TPO foam preform, rapidly cooling the die and the TPO foam product therein after the pressing is finished, finally opening the die, and taking out the TPO foam product subjected to the press molding.
The density of the final compression molded TPO foam article was measured to be 0.12g/cm 3 The thickness of the compact skin layer of the foam product is 5 microns, the equivalent spherical diameter of the second-stage cells is 1.8mm, the wall thickness of the second-stage cells is 8 microns, and the equivalent spherical diameter of the third-stage cells is 100 microns; the foam product had a ball rebound coefficient of 65%, a tensile strength of 2.4MPa, an elongation at break of 200%, and a tear strength of 1.6kg/cm 2 And a permanent compression set of 32%.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A polymeric foam article having a hierarchical cell structure, wherein an outer surface of said polymeric foam article has a dense, unfoamed skin structure, said skin structure constituting a first level cell structure of said polymeric foam article; a second-stage cellular structure exists inside the skin layer structure, and the inside of the skin layer structure is composed of the second-stage cellular structure; a third-stage cellular structure exists inside the second-stage cellular structure, the inside of the second-stage cellular structure is composed of the third-stage cellular structure, and the thickness of the skin layer structure ranges from 2 micrometers to 500 micrometers; the equivalent sphere diameter range of the second-stage cellular structure is 0.5 mm-10 mm, and the wall thickness range is 0.5 μm-50 μm; the equivalent spherical diameter range of the third-stage cellular structure is 5-500 mu m.
2. The polymeric foam article having a hierarchical cell structure according to claim 1, wherein the skin structure has a thickness in a range from 10 μ ι η to 100 μ ι η.
3. The polymeric foam article having a hierarchical cell structure according to claim 1, wherein the second stage cell structure has an equivalent spherical diameter ranging from 2mm to 8mm and a wall thickness ranging from 5 μ ι η to 30 μ ι η.
4. The polymeric foam article having a hierarchical cell structure according to claim 1 wherein the equivalent spherical diameter of the third stage cells ranges from 20 μ ι η to 200 μ ι η.
5. The method of any one of claims 1 to 4 for preparing a polymeric foam article having a hierarchical cell structure, comprising the steps of:
(1) sintering and molding the thermoplastic elastomer bead foam at one time to obtain a prefabricated blank with a certain shape and structure;
(2) and placing the prefabricated blank into a mould for secondary sintering molding, rapidly heating the mould, closing the mould to press the prefabricated blank, and rapidly cooling the mould after the pressing molding so as to cool and shape the polymer foam product in the mould.
6. The preparation method according to claim 5, wherein the thermoplastic elastomer is one or more of thermoplastic polyurethane, thermoplastic polyester elastomer, thermoplastic nylon elastomer, olefinic elastomer and polybutylene adipate terephthalate; preferably, the olefinic elastomer is one or more of TPO, TPV or POE.
7. Preparation according to claim 5The method is characterized in that the equivalent spherical diameter of the thermoplastic elastomer bead foam is in the range of 0.5mm to 10mm, more preferably in the range of 2mm to 8mm, and the density of the bead foam is 0.05g/cm 3 ～0.18g/cm 3 Further, it is preferable that the density is in the range of 0.08g/cm 3 ～0.15g/cm 3 。
8. The method according to claim 5, wherein the primary sintering molding is steam heating molding or microwave heating molding, and the temperature range of the primary sintering molding is 100 ℃ to 160 ℃, and the further preferred sintering temperature range is 110 ℃ to 140 ℃.
9. The production method according to claim 5, wherein the secondary sintering molding rapidly heats the mold to a temperature of 110 to 180 ℃.
10. The method according to claim 9, wherein the mold temperature in the secondary sintering molding is in the range of 120 ℃ to 160 ℃.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172622A (en) * | 1996-08-01 | 1998-02-11 | 成信新素材株式会社 | Process for manufacturing midsole/sole |
| US20140017450A1 (en) * | 2012-07-10 | 2014-01-16 | Nike, Inc. | Bead Foam Compression Molding Method for Low Density Product |
| CN107599292A (en) * | 2017-08-25 | 2018-01-19 | 晋江创赢新材料科技有限公司 | A kind of processing technology of appearance densification ETPU damping midsoles |
| KR101839434B1 (en) * | 2017-02-13 | 2018-04-26 | 화인케미칼 주식회사 | Method of manufacturing midsole |
| CN108472843A (en) * | 2016-01-18 | 2018-08-31 | 库尔兹股份有限公司 | Method and apparatus for manufacturing particle foam component |
| US20190256680A1 (en) * | 2016-11-11 | 2019-08-22 | Jsp Corporation | Foam particles, and moulded article thereof |
| CN110328796A (en) * | 2019-06-28 | 2019-10-15 | 武汉理工大学 | A kind of preparation method of polymer matrix fretting map interlayer functionally gradient material (FGM) |
| CN111205504A (en) * | 2020-03-19 | 2020-05-29 | 福建鑫瑞新材料科技有限公司 | Thermoplastic elastomer bead foam and preparation method thereof |
| CN111515395A (en) * | 2020-04-09 | 2020-08-11 | 安徽省新方尊自动化科技有限公司 | Foam metal with hierarchical pore structure, preparation method thereof and sound absorption and noise reduction material |
| CN113271803A (en) * | 2018-12-06 | 2021-08-17 | 耐克创新有限合伙公司 | Method for manufacturing articles using foam particles |
| CN113308018A (en) * | 2021-07-09 | 2021-08-27 | 无锡会通轻质材料股份有限公司 | Preparation method of low-thermal-conductivity expanded polypropylene beads |
| CN113372605A (en) * | 2021-04-26 | 2021-09-10 | 无锡会通轻质材料股份有限公司 | Expandable polylactic acid composite particles with core-shell structure, expanded beads and preparation method of molded part of expanded beads |
| CN113631655A (en) * | 2018-06-29 | 2021-11-09 | 陶氏环球技术有限责任公司 | Foam bead and sintered foam structure |
-
2022
- 2022-07-11 CN CN202210809329.7A patent/CN115044189A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172622A (en) * | 1996-08-01 | 1998-02-11 | 成信新素材株式会社 | Process for manufacturing midsole/sole |
| US20140017450A1 (en) * | 2012-07-10 | 2014-01-16 | Nike, Inc. | Bead Foam Compression Molding Method for Low Density Product |
| CN108472843A (en) * | 2016-01-18 | 2018-08-31 | 库尔兹股份有限公司 | Method and apparatus for manufacturing particle foam component |
| US20190256680A1 (en) * | 2016-11-11 | 2019-08-22 | Jsp Corporation | Foam particles, and moulded article thereof |
| KR101839434B1 (en) * | 2017-02-13 | 2018-04-26 | 화인케미칼 주식회사 | Method of manufacturing midsole |
| CN107599292A (en) * | 2017-08-25 | 2018-01-19 | 晋江创赢新材料科技有限公司 | A kind of processing technology of appearance densification ETPU damping midsoles |
| CN113631655A (en) * | 2018-06-29 | 2021-11-09 | 陶氏环球技术有限责任公司 | Foam bead and sintered foam structure |
| CN113271803A (en) * | 2018-12-06 | 2021-08-17 | 耐克创新有限合伙公司 | Method for manufacturing articles using foam particles |
| CN110328796A (en) * | 2019-06-28 | 2019-10-15 | 武汉理工大学 | A kind of preparation method of polymer matrix fretting map interlayer functionally gradient material (FGM) |
| CN111205504A (en) * | 2020-03-19 | 2020-05-29 | 福建鑫瑞新材料科技有限公司 | Thermoplastic elastomer bead foam and preparation method thereof |
| CN111515395A (en) * | 2020-04-09 | 2020-08-11 | 安徽省新方尊自动化科技有限公司 | Foam metal with hierarchical pore structure, preparation method thereof and sound absorption and noise reduction material |
| CN113372605A (en) * | 2021-04-26 | 2021-09-10 | 无锡会通轻质材料股份有限公司 | Expandable polylactic acid composite particles with core-shell structure, expanded beads and preparation method of molded part of expanded beads |
| CN113308018A (en) * | 2021-07-09 | 2021-08-27 | 无锡会通轻质材料股份有限公司 | Preparation method of low-thermal-conductivity expanded polypropylene beads |
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