CN111205504B - Thermoplastic elastomer bead foam and preparation method thereof - Google Patents
Thermoplastic elastomer bead foam and preparation method thereof Download PDFInfo
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- CN111205504B CN111205504B CN202010194144.0A CN202010194144A CN111205504B CN 111205504 B CN111205504 B CN 111205504B CN 202010194144 A CN202010194144 A CN 202010194144A CN 111205504 B CN111205504 B CN 111205504B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- 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
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/26—Elastomers
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Abstract
The invention relates to thermoplastic elastomer bead foam, in particular to thermoplastic elastomer bead foam and a preparation method thereof. The elastomer bead foam comprises large cells and small cells, and the diameter of the large cells is larger than that of the small cells. The preparation method comprises the following steps: mixing gas into the thermoplastic elastomer melt in the process of extruding the granules to obtain thermoplastic elastomer granules containing the large cells; adding the obtained thermoplastic elastic particles into a foaming agent, and obtaining the thermoplastic elastic bead foam with the heterogeneous cell structure comprising the large cells and the small cells by a batch kettle pressure foaming method. The foam of the present invention can significantly reduce the overall density of the bead foam by increasing the presence of large cells, thereby achieving the goals of improved lightweighting and reduced material consumption.
Description
Technical Field
The invention relates to thermoplastic elastomer bead foam, in particular to thermoplastic elastomer bead foam and a preparation method thereof.
Background
Thermoplastic elastomer bead foams are a type of granular thermoplastic elastomer foams having a porous structure prepared by a physical or chemical foaming process using a granular thermoplastic elastomer (e.g., Thermoplastic Polyurethane (TPU), thermoplastic Polyamide Elastomer (PEBA), thermoplastic polyester elastomer (TPEE), etc.) as a raw material. The thermoplastic elastomer bead foam has the characteristics of high elasticity, high strength, low temperature resistance, recyclability, easiness in molding and processing and the like, and has wide application prospects in the fields of shoe materials, sports goods, safety protection, noise elimination and shock absorption and the like.
Currently, batch foaming processes and extrusion foaming processes using physical blowing agents (including carbon dioxide, nitrogen, butane, pentane, etc.) are the two main methods for preparing thermoplastic elastomer bead foams. In general, the thermoplastic elastomer bead foam prepared by the above two physical foaming processes has a homogeneous cell structure, which causes the following problems:
(1) the density of the bead foam is relatively high, which not only is not favorable for the light weight of the product, but also increases the material cost;
(2) after the post-steam molding, the bonding strength between bead foams is not high, resulting in poor durability of products processed by bead foam molding.
Disclosure of Invention
Technical problem to be solved
In order to solve the above problems of the prior art, the present invention provides a thermoplastic elastomer bead foam having a heterogeneous cell structure, which includes both large cells and small cells, and has the advantages of low relative density, high bonding strength between foams, and high elasticity.
Correspondingly, the invention also provides the corresponding thermoplastic elastomer bead foam with the heterogeneous cell structure, which is obtained by using a particle extrusion method and a batch kettle pressure foaming method.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
the invention provides a thermoplastic elastomer bead foam with a heterogeneous cell structure, wherein the elastomer bead foam comprises large cells and small cells, and the diameter of the large cells is larger than that of the small cells.
Furthermore, the diameter of the large foam hole is 0.5-12 mm;
or/and
the diameter of the small foam hole is 0.01-0.2 mm.
Furthermore, more than two small foam holes are distributed around the adjacent large foam holes.
Furthermore, more than 1 large cell is distributed in the bead foam per cubic millimeter.
The invention also provides a preparation method of the thermoplastic elastomer bead foam with the heterogeneous cell structure, which comprises the following steps:
s1, mixing gas into the thermoplastic elastomer melt in the process of extruding particles to obtain thermoplastic elastomer particles containing large cells;
s2 adding the obtained thermoplastic elastomer particles into a foaming agent, and obtaining the thermoplastic elastomer bead foam with a heterogeneous cell structure comprising large cells and small cells by a batch kettle pressure foaming method.
Further, in step S1, nitrogen or air is mixed into the thermoplastic elastomer melt in a mass fraction of 0.05% to 0.2%, or carbon dioxide gas is mixed into the thermoplastic elastomer melt in a mass fraction of 0.1% to 3%, during the extrusion of the thermoplastic elastomer melt through the extruder.
Further, in step S2, the blowing agent is carbon dioxide.
Further, in step S2, placing the thermoplastic elastomer particles into an autoclave, introducing carbon dioxide until the pressure is 10 to 30MPa, adjusting the temperature of the autoclave to be within 120 to 160 ℃ and keeping the temperature for 10 to 60min, and then rapidly discharging the high-pressure carbon dioxide gas in the autoclave to induce foaming, thereby obtaining the thermoplastic elastomer bead foam.
(III) advantageous effects
The invention has the beneficial effects that:
1. the foam of the present invention can significantly reduce the overall density of the bead foam by increasing the presence of larger cells, thereby achieving the goals of improved light weight and reduced material consumption.
2. The obtained foam with the heterogeneous cell structure is different from the bead foam with the homogeneous cell structure in the prior art, the density distribution of the bead foam is obviously uneven due to the existence of large cells and small cells, the foam has lower density in the large cell area and higher density in the small cell area, when the bead foam is subjected to thermoplastic molding, the bead foam is bonded together through the small cells, and the foam has higher bonding strength due to the fact that the diameter of the small cells is much smaller than the cells of the homogeneous cell structure in the prior art and the density of the foam at the small cells is high, namely, the overall density is reduced and the adhesiveness between the bead foam can be improved through the arrangement of the large cells and the small cells.
3. Due to the staggered arrangement of the large foam hole and the small foam hole, the obtained foam has stronger elasticity.
Drawings
FIG. 1 is a view of virgin thermoplastic elastomer particles that have not been subjected to the inventive treatment;
FIG. 2 is a view showing thermoplastic elastomer particles comprising only large cells in the present invention;
FIG. 3 is a thermoplastic elastomer bead foam of the present invention having a heterogeneous cell structure comprising both large and small cells.
Reference numerals:
1-large cells; 2 small cells.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention by way of specific embodiments thereof.
[ first embodiment ] to provide a toner
As shown in fig. 3, the present embodiment provides a thermoplastic elastomer bead foam having a heterogeneous cell structure, the elastomer bead foam including large cells and small cells, the large cells having a diameter larger than that of the small cells.
The embodiment reduces the overall density of the thermoplastic elastomer bead foam by arranging the large bubble holes 1 and the small bubble holes 2, and simultaneously improves the elasticity of the thermoplastic elastomer bead foam due to the compression or amplification interaction between the air in different pore diameters of the large bubble holes and the air in different pore diameters of the small bubble holes.
To improve adhesion between adjacent foams, more than two small cells are distributed around between adjacent large cells. This allows adjacent foams to be bonded together with a higher adhesion due to the higher density of the foam at the cell sites.
In order to optimize the synergistic promotion effect between the large cells and the small cells of the thermoplastic elastomer bead foam in the embodiment, the diameter of the large cells is 0.5-12 mm;
or/and
the diameter of the small bubble hole is 0.01-0.2 mm.
The range of the diameters of the small cells is not essential, but the smaller the diameter of the small cells, the larger the number of the small cells, the more the density of the whole is reduced, the more the elasticity of the foam is increased, and the adhesion between the adjacent foams is increased.
Preferably, in the foam with the diameter of 2-15 mm, 1-10 large foam holes with the diameter of 0.5-12 mm are distributed in the foam in a scattered manner, and more than 2 small foam holes with the diameter of 0.01-0.2 mm are distributed between the adjacent large foam holes. The density of the obtained foam is 0.05-0.3 g/cm 3 。
Preferably, in the foam with the diameter of 4-10 mm, 4-6 large foam holes with the diameter of 2-4 mm are distributed in the foam in a scattered manner, and more than 2 small foam holes with the diameter of 0.03-0.08 mm are distributed between the adjacent large foam holes.
In order to provide the thermoplastic elastomer bead foam of this embodiment with better resilience and suitably lower overall density. More than 1 large cell is distributed in the bead foam per cubic millimeter.
[ second embodiment ] to provide a medicine for treating diabetes
The present embodiment provides a method for preparing a thermoplastic elastomer bead foam having a heterogeneous cell structure, comprising the steps of:
s1, mixing gas into the granules shown in the figure 1 through preparing the thermoplastic elastomer melt at high temperature in the process of extruding the granules to obtain thermoplastic elastomer granules containing large cells;
s2 adding the obtained thermoplastic elastomer particles into a foaming agent, and obtaining the thermoplastic elastomer bead foam with a heterogeneous cell structure comprising large cells and small cells by a batch kettle pressure foaming method.
In this embodiment, thermoplastic elastomer particles having large cells are obtained by an extruder extrusion method. As shown in fig. 2. And combining with a batch kettle pressure foaming method to obtain the foam with large foam holes and small foam holes simultaneously. Uniform small foam holes can be obtained on the premise of not damaging large foam holes, and the yield is more than 99%.
Further, in step S1, during the extrusion of the thermoplastic elastomer melt through the extruder, nitrogen or air is mixed into the thermoplastic elastomer melt in an amount of 0.05 to 0.2% by mass, or carbon dioxide gas is mixed into the thermoplastic elastomer melt in an amount of 0.1 to 3% by mass.
By adding the gas in the proportion, the diameter of the obtained large foam hole can be in the range of 0.5-12 mm.
Further, the foaming agent in step S2 is carbon dioxide.
Further, in step S2, placing the thermoplastic elastomer particles into an autoclave, introducing carbon dioxide until the pressure is 10 to 30MPa, adjusting the temperature of the autoclave to be within 120 to 160 ℃ and keeping the temperature for 10 to 60min, and then rapidly discharging the high-pressure carbon dioxide gas in the autoclave to induce foaming, thereby obtaining the thermoplastic elastomer bead foam. By the method, small cells can be successfully obtained, large cells are not destroyed, and the yield of foam is high.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
Thermoplastic elastomer bead foam having a heterogeneous cell structure with 7mm diameter having 2 large cells of 3mm diameter and 10 small cells of 0.08mm between adjacent large cells.
Example 2
A thermoplastic elastomer bead foam having a heterogeneous cell structure, which has a diameter of 15mm, 10 large cells having a diameter of 0.8mm are arranged, and 20 small cells having a diameter of 0.02mm are arranged between adjacent large cells.
Example 3
Thermoplastic elastomer bead foam having a heterogeneous cell structure with 3mm diameter, 4 large cells of 0.6mm diameter and 3 small cells of 0.18mm between adjacent large cells.
Example 4
The preparation method of the thermoplastic elastomer bead foam specifically comprises the following steps:
after the pellets shown in FIG. 1 were produced into a thermoplastic elastomer melt at a high temperature by means of a single-screw or twin-screw extruder, nitrogen gas was mixed into the thermoplastic elastomer melt at a mass fraction of 0.18% through a hopper, a cylinder or a die, thereby obtaining thermoplastic elastomer pellets shown in FIG. 2 having large cells in the interior thereof after cooling and pelletizing the extrudate. Putting the obtained thermoplastic elastomer particles as raw materials into an autoclave; and (2) introducing carbon dioxide gas into the high-pressure kettle until the pressure of the carbon dioxide gas in the high-pressure kettle is stabilized at 20MPa, controlling the temperature in the kettle within the range of 140 ℃ by using a temperature control device matched with the high-pressure kettle, keeping the temperature for 30min, and quickly discharging the high-pressure carbon dioxide gas in the kettle by opening an exhaust valve or the high-pressure kettle so as to induce foaming to prepare the thermoplastic elastomer bead foam which simultaneously comprises large cells and small cells and has the heterogeneous cell structure as shown in the figure 3.
Example 5
The preparation method of the thermoplastic elastomer bead foam comprises the following specific steps:
after the pellets shown in FIG. 1 were produced into a thermoplastic elastomer melt at a high temperature by means of a single-screw or twin-screw extruder, carbon dioxide gas was mixed into the thermoplastic elastomer melt at a mass fraction of 0.15% through a hopper, a cylinder or a die, thereby obtaining thermoplastic elastomer pellets shown in FIG. 2 having large cells in the interior thereof after cooling and pelletizing the extrudate. Putting the obtained thermoplastic elastomer particles as a raw material into an autoclave; and (3) introducing carbon dioxide gas into the high-pressure kettle until the pressure of the carbon dioxide gas in the high-pressure kettle is stabilized at 30MPa, controlling the temperature in the kettle at 160 ℃ for 20min by using a temperature control device matched with the high-pressure kettle, and quickly discharging the high-pressure carbon dioxide gas in the kettle by opening an exhaust valve or the high-pressure kettle so as to induce foaming to prepare the thermoplastic elastomer bead foam which simultaneously contains large cells and small cells and has the heterogeneous cell structure as shown in the figure 3.
Example 6
The preparation method of the thermoplastic elastomer bead foam specifically comprises the following steps:
after the pellets shown in fig. 1 were produced into a thermoplastic elastomer melt at a high temperature by means of a single-screw or twin-screw extruder, carbon dioxide gas was mixed into the thermoplastic elastomer melt at a mass fraction of 3% through a hopper, a cylinder or a die, thereby obtaining thermoplastic elastomer pellets shown in fig. 2 containing large cells inside after cooling and pelletizing the extrudate. Putting the obtained thermoplastic elastomer particles as a raw material into an autoclave; and (3) introducing carbon dioxide gas into the high-pressure autoclave until the pressure of the carbon dioxide gas in the high-pressure autoclave is stabilized within the range of 10MPa, controlling the temperature in the autoclave within the range of 120 ℃ for 20min by using a temperature control device matched with the high-pressure autoclave, and then quickly discharging the high-pressure carbon dioxide gas in the autoclave by opening an exhaust valve or the high-pressure autoclave so as to induce foaming to prepare the thermoplastic elastomer bead foam which simultaneously contains large cells and small cells and has the heterogeneous cell structure shown in figure 3.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (3)
1. A method of preparing a thermoplastic elastomer bead foam, characterized by: the thermoplastic elastomer bead foam comprises large cells and small cells, and the diameter of the large cells is larger than that of the small cells; the diameter of the large foam hole is 0.5-12 mm;
or/and
the diameter of the small foam hole is 0.01-0.2 mm;
more than two small foam holes are distributed around the adjacent large foam holes;
more than 1 large cell is distributed in each cubic millimeter of bead foam;
the preparation method of the thermoplastic elastomer bead foam comprises the following steps:
s1, mixing gas into the thermoplastic elastomer melt in the process of extruding particles to obtain thermoplastic elastomer particles containing the large cells;
s2, adding the obtained thermoplastic elastic particles into a foaming agent, and obtaining thermoplastic elastomer bead foam with a heterogeneous cell structure containing the large cells and the small cells by a batch kettle pressure foaming method;
in step S1, nitrogen or air with the mass fraction of 0.05-0.2% or carbon dioxide with the mass fraction of 0.1-3% is mixed into the thermoplastic elastomer melt in the process of extruding the thermoplastic elastomer melt through an extruder.
2. The method of claim 1, wherein in step S2, the blowing agent is carbon dioxide.
3. A process for preparing a thermoplastic elastomer bead foam according to claim 1, wherein: in step S2, the thermoplastic elastomer particles are placed in an autoclave, carbon dioxide is introduced until the pressure is 10-30 MPa, the temperature of the autoclave is adjusted within the range of 120-160 ℃ and kept for 10-60 min, then the high-pressure carbon dioxide gas in the autoclave is rapidly discharged to induce foaming, and the thermoplastic elastomer bead foam is obtained.
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| CN115044189A (en) * | 2022-07-11 | 2022-09-13 | 福建鑫瑞新材料科技有限公司 | Polymer foam product with hierarchical pore structure and preparation method thereof |
| CN116960546B (en) * | 2023-09-13 | 2024-01-30 | 湖北祥源高新科技有限公司 | Organic silicon foaming material and battery module comprising same |
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| CN102321268A (en) * | 2011-08-04 | 2012-01-18 | 南京法宁格节能科技有限公司 | Method for producing polyvinyl chloride rigid foam plastics by carbon dioxide foaming agent |
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Denomination of invention: Thermoplastic elastomer bead foam and its preparation method Effective date of registration: 20230925 Granted publication date: 20220906 Pledgee: China Co truction Bank Corp Xianyou branch Pledgor: FUJIAN XINRUI NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2023350000208 |