CN111718514A - Preparation process of ultralight thermoplastic elastomer foam material - Google Patents
Preparation process of ultralight thermoplastic elastomer foam material Download PDFInfo
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- CN111718514A CN111718514A CN202010406242.6A CN202010406242A CN111718514A CN 111718514 A CN111718514 A CN 111718514A CN 202010406242 A CN202010406242 A CN 202010406242A CN 111718514 A CN111718514 A CN 111718514A
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000006261 foam material Substances 0.000 title claims description 8
- 238000005187 foaming Methods 0.000 claims abstract description 55
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 38
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 31
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 229920001971 elastomer Polymers 0.000 claims abstract description 19
- 239000000806 elastomer Substances 0.000 claims abstract description 19
- 239000013067 intermediate product Substances 0.000 claims abstract description 16
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 19
- 229920002614 Polyether block amide Polymers 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000000034 method Methods 0.000 abstract description 4
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- C08J9/04—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
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a preparation process of an ultralight thermoplastic elastomer foaming material, which comprises the following steps of ① putting a thermoplastic polyurethane elastomer into a first reaction kettle, introducing carbon dioxide for first supercritical foaming, releasing pressure to obtain a foaming intermediate product, ② putting the foaming intermediate product into a second reaction kettle, introducing nitrogen for second supercritical foaming, and releasing pressure to obtain a foaming material with the density of 0.05-0.1g/cm3The foamed product of (4). Compared with the prior art, the invention adopts a two-step method, the first step adopts carbon dioxide for nucleation, and the second step adopts nitrogen for foaming, so that the foaming material with extremely low density, small shrinkage, good elasticity and stable performance can be obtained.
Description
Technical Field
The invention relates to the field of thermoplastic elastomer foaming, in particular to a preparation process of an ultralight thermoplastic elastomer foaming material, wherein the ultralight refers to the density of 0.1g/cm3The following foamed product.
Background
In recent years, supercritical foaming materials and the technology thereof are exploded in the market, and especially supercritical foaming of elastomers has very wide application prospect in the fields of sports shoes, sports equipment and shock absorption and noise reduction because of the advantages of high resilience, low density, good molding processability and the like.
Many research institutions and companies are currently doing much work in the direction of supercritical foaming of elastomers. However, despite much research work, a problem remains with the preparation of ultra low density elastomeric materials, such as CO2Is carried out as a blowing agentThe foaming material with lower initial density can be obtained by supercritical foaming, but after foaming, because the pressure difference exists between carbon dioxide in the foam holes and outside air, the diffusion speed of the carbon dioxide is far higher than the compensation speed of the outside air, so that the elastomer foaming material is rapidly shrunk, a large amount of shrinkage wrinkles exist on the surface of the final foaming material, the final density is higher, the performance is also lost, and the application value is lost.
In order to solve the shrinkage problem, chinese patent documents CN103642200A and CN108239385A use TPU as main raw material, and add different polymers and compatibilizers to improve the shrinkage problem after foaming TPU.
In addition, chinese patent document CN108239385A discloses a thermoplastic polyurethane foamed particle and a preparation method thereof, which is a blended alloy particle obtained by blending thermoplastic polyurethane elastomer as a main raw material with a certain component of thermoplastic resin polymer and a compatibilizer. Then, the TPU foaming particles are foamed by carbon dioxide, so that the TPU foaming particles are more stable in size, the surfaces are bright and full, and the resilience is improved.
Other Chinese patent documents CN110951258A, CN110791088A and CN108250734A respectively use EVA/TPU, PA/TPU and PEBAX/TPU as raw materials to carry out supercritical foaming, and the density of the raw materials is 0.17g/cm3Above, currently, the elastomer material is required to be 0.1g/cm3Products of the following densities have certain difficulties. However, the ultra-low density products have a large market in the fields of heat preservation, weight reduction, buffering, packaging and the like.
Based on this, the applicant has diligently studied the above problems and made the present invention.
Disclosure of Invention
The invention mainly aims to provide a preparation process of an ultralight thermoplastic elastomer foaming material, which can be used for forming the ultralight foaming material with stable performance, and the density of the formed foaming material is 0.05-0.10.1g/cm3。
In order to achieve the above purpose, the solution of the invention is:
a preparation process of an ultralight thermoplastic elastomer foaming material comprises the following steps:
firstly, putting a thermoplastic polyurethane elastomer into a first reaction kettle, introducing carbon dioxide for carrying out first supercritical foaming, and releasing pressure to obtain a foaming intermediate product;
② placing the intermediate product into the second reaction kettle, introducing nitrogen gas for the second supercritical foaming, and releasing pressure to obtain product with density of 0.05-0.1g/cm3The foamed product of (4).
Further, the thermoplastic polyurethane elastomer is a sheet formed by extruding, molding or injection molding the TPU, the TPEE, the PEBAX, the TPU/PEBAX blend, the TPU/TPEE blend or the TPEE/PEBAX blend.
Further, the saturation pressure, saturation temperature and saturation time in the first supercritical foaming are all smaller than the saturation pressure, saturation temperature and saturation time in the second supercritical foaming.
Furthermore, the saturation temperature of the first supercritical foaming is 100-160 ℃, the saturation pressure is 7-10MPa, and the saturation time is 0.5-4 h; the saturation temperature of the second supercritical foaming is 120-170 ℃, the saturation pressure is 10-30Mpa, and the saturation time is 2-10 h.
Further, during the first supercritical foaming, the saturation temperature of the TPEE material carbon dioxide is 110-.
Further, during the second supercritical foaming, the saturation temperature of the TPEE nitrogen is 120-150 ℃, the saturation temperature of the TPU nitrogen is 140-170 ℃, the saturation temperature of the PEBAX nitrogen is 120-150 ℃, and the temperature range of the mixture is between the temperature range of the mixture of the two.
Further, the density of the foamed intermediate product is 0.3 to 0.5g/cm3。
After the structure is adopted, the invention relates to a preparation process of an ultralight thermoplastic elastomer foaming material, which is an intelligent crystal obtained after comprehensive analysis of carbon dioxide supercritical foaming and nitrogen supercritical foaming. The product obtained by normal foaming of carbon dioxide gas has low density but large shrinkage; the product foamed with nitrogen is dense but stable without shrinkage.
First, CO2The lower density of energy is due to its greater solubility in the polymer and the greater shrinkage is due to the CO2Too different from air in diffusion coefficient; n is a radical of2Solubility in polymer less than CO2So that the density of the foamed product is relatively high, and N2The diffusion coefficient of (a) is almost the same as that of air, so that the foamed product is dimensionally stable and is not easily shrunk.
The invention adopts a two-step method, firstly utilizes CO2High solubility, forming a large number of gas nuclei in the elastomeric polymer, ensuring the polymer to be microfoamed by controlling the temperature and pressure of the reactor, and then introducing N2，N2Prior to occupation of CO2After saturation, the pressure is quickly released, and the bubble core grows up to obtain the elastomer material with ultralow density.
The main principle of the invention is as follows: the diffusion rate of nitrogen and air is almost the same, and the method is more suitable for elastomer foaming. However, the nitrogen has low solubility in the polymer, poor plasticizing effect on the polymer and low nucleation rate, and results in large foaming density and large cells. If the cell size of the TPU in comparative example 1 is 120um and the density is 0.183, carbon dioxide has a very strong plasticizing effect on the elastomer, and a lower initial density can be obtained after foaming, if the TPU is foamed by carbon dioxide, the density is 0.108g/cm3However, shrinkage occurred rapidly, and the surface had shrinkage wrinkles as shown in FIG. 3, and the density became 0.256g/cm after standing for 6 hours3Fig. 4 shows the variation curve.
Compared with the prior art, the invention adopts a two-step method, the first step adopts carbon dioxide for nucleation, and the second step adopts nitrogen for foaming, so that the foaming material with extremely low density, small shrinkage, good elasticity and stable performance can be obtained.
Drawings
FIG. 1 is a scanning electron micrograph of a foamed elastomer obtained in comparative example 1;
FIG. 2 is a graph showing the change in density of the foamed elastomer obtained in comparative example 1 with respect to the standing time;
FIG. 3 is a photograph of the foamed elastomer obtained in comparative example 2 after shrinking;
FIG. 4 is a graph showing the change in density of the foamed elastomer obtained in comparative example 2 with respect to the standing time;
FIG. 5 is a scanning electron micrograph of a primary foamed intermediate of example 1;
FIG. 6 is a scanning electron micrograph of the final foamed product of example 1;
FIG. 7 is a scanning electron micrograph of the final foamed product of example 2.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Comparative example 1:
putting the TPU plate into a supercritical reaction kettle of nitrogen, wherein the temperature in the kettle is 155 ℃, the pressure in the kettle is 22Mpa, the TPU plate is saturated for 4 hours, and the foamed elastomer sample with the density of 0.183g/cm is obtained after pressure relief3The rebound was 65%, and the scanning electron micrograph thereof is shown in FIG. 1, wherein the average cell size is 120. mu.m, and the cell density is 4.18 × 104 cells ls/cm3。
N2The density of the foamed material as a function of the standing time is shown in FIG. 2.
Comparative example 2:
putting the TPU plate into a carbon dioxide supercritical reaction kettle, wherein the temperature in the kettle is 155 ℃, the pressure is 18Mpa, the TPU plate is saturated for 2 hours, a foaming elastomer sample is obtained after pressure relief, and the density of a newly-developed product is 0.108g/cm3And the density is 0.254g/cm after standing for 3 hours3The surface of the board after shrinkage has a plurality of wrinkles, the original properties such as elasticity and low density are lost, the picture after shrinkage is shown in figure 3, CO2The density of the foamed material as a function of the standing time is shown in FIG. 4.
Example 1:
putting the TPU plate into a supercritical reaction kettle, introducing carbon dioxide for saturation at the saturation pressure of 10MPa and the saturation temperature of 140 ℃ for 2 hours, and then quickly releasing the pressure to obtain the TPU plate with the density of 0.461g/cm3The foaming intermediate product is put into a supercritical reaction kettle, nitrogen is introduced for saturation, the saturation pressure is 22MPa, and the saturation temperature is highThe temperature is 160 ℃, the saturation time is 4 hours, the pressure is released quickly after the saturation is finished, and the density is 0.088g/cm3The foamed product of (1), after standing for 6 hours, had a final density of 0.092g/cm3The rebound was 75%, the cell size was 97um, and the cell density was 2.82 × 107 cells ls/cm3。
Example 2
Putting the TPEE sheet into a supercritical reaction kettle, introducing carbon dioxide for saturation at the saturation pressure of 10MPa and the saturation temperature of 130 ℃ for 2 hours, and then quickly releasing the pressure to obtain the TPEE sheet with the density of 0.362g/cm3The foamed intermediate product is put into a supercritical reaction kettle, nitrogen is introduced for saturation, the saturation pressure is 22MPa, the saturation temperature is 150 ℃, the saturation time is 4 hours, the pressure is rapidly released after the saturation is finished, and the density is 0.068g/cm3The foamed product of (1) has a final density of 0.071g/cm after standing for 6 hours3The rebound was 83%.
Example 3:
putting the PEBAX shoe insole board into a supercritical reaction kettle, introducing carbon dioxide for saturation at a saturation pressure of 10MPa and a saturation temperature of 125 ℃ for 2 hours, and then rapidly releasing the pressure to obtain the PEBAX shoe insole board with a density of 0.358g/cm3The foamed intermediate product is put into a supercritical reaction kettle, nitrogen is introduced for saturation, the saturation pressure is 22MPa, the saturation temperature is 145 ℃, the saturation time is 6 hours, and the pressure is rapidly released after the saturation is finished to obtain the density of 0.060g/cm3The foamed product of (1) has a final density of 0.063g/cm after standing for 6 hours3The rebound was 85%.
Example 4:
putting the TPU/TPEE blended insole board (wherein the proportion of TPU is 80 percent, the proportion of TPEE is 20 percent) into a supercritical reaction kettle, introducing carbon dioxide for saturation, wherein the saturation pressure is 12MPa, the saturation temperature is 138 ℃, the saturation time is 3 hours, and then quickly releasing the pressure to obtain the density of 0.403g/cm3The foamed intermediate product is put into a supercritical reaction kettle, nitrogen is introduced for saturation, the saturation pressure is 24MPa, the saturation temperature is 150 ℃, the saturation time is 6 hours, the pressure is rapidly released after the saturation is finished, and the density is 0.086g/cm3The foamed product of (a) is,the final density after standing for 6h is 0.089g/cm3The rebound was 77%.
Example 5:
putting the TPU/PEBAX blended plate (wherein the TPU accounts for 75 percent, and the PEBAX accounts for 25 percent) into a supercritical reaction kettle, introducing carbon dioxide for saturation, wherein the saturation pressure is 11MPa, the saturation temperature is 132 ℃, the saturation time is 2 hours, and then quickly releasing the pressure to obtain the plate with the density of 0.384g/cm3The foamed intermediate product is put into a supercritical reaction kettle, nitrogen is introduced for saturation, the saturation pressure is 25MPa, the saturation temperature is 148 ℃, the saturation time is 6 hours, and the pressure is quickly released after the saturation is finished to obtain the foamed intermediate product with the density of 0.081g/cm3The foamed product of (1), after standing for 6 hours, had a final density of 0.084g/cm3The rebound was 79%.
Example 6:
putting the TPEE/TPU blended plate (wherein the proportion of TPEE is 60 percent and the proportion of TPU is 40 percent) into a supercritical reaction kettle, introducing carbon dioxide for saturation, wherein the saturation pressure is 11MPa, the saturation temperature is 130 ℃, the saturation time is 2 hours, and then quickly releasing the pressure to obtain the TPEE/TPU blended plate with the density of 0.426g/cm3The foaming intermediate product is put into a supercritical reaction kettle, nitrogen is introduced for saturation, the saturation pressure is 25MPa, the saturation temperature is 148 ℃, the saturation time is 6 hours, the pressure is rapidly released after the saturation is finished, and the density is 0.075g/cm3The foamed product of (1) has a final density of 0.078g/cm after standing for 6 hours3The rebound was 80%.
Example 7:
putting the TPEE/PEBAX blended plate (wherein the proportion of TPEE is 50 percent and the proportion of PEBAX is 50 percent) into a supercritical reaction kettle, introducing carbon dioxide for saturation at the saturation pressure of 14MPa and the saturation temperature of 125 ℃ for 2 hours, and then quickly releasing pressure to obtain the plate with the density of 0.311g/cm3The foamed intermediate product is put into a supercritical reaction kettle, nitrogen is introduced for saturation, the saturation pressure is 28MPa, the saturation temperature is 140 ℃, the saturation time is 6 hours, the pressure is rapidly released after the saturation is finished, and the density is 0.058g/cm3The foamed product of (1) has a final density of 0.061g/cm after being placed for 6 hours3The rebound was 85%.
The above embodiments and drawings are not intended to limit the form and style of the present invention, and any suitable changes or modifications thereof by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (7)
1. A preparation process of an ultralight thermoplastic elastomer foaming material is characterized by comprising the following steps:
firstly, putting a thermoplastic polyurethane elastomer into a first reaction kettle, introducing carbon dioxide for carrying out first supercritical foaming, and releasing pressure to obtain a foaming intermediate product;
② placing the intermediate product into the second reaction kettle, introducing nitrogen gas for the second supercritical foaming, and releasing pressure to obtain product with density of 0.05-0.1g/cm3The foamed product of (4).
2. The process for preparing an ultralight thermoplastic elastomer foam material according to claim 1, wherein the thermoplastic polyurethane elastomer is a sheet formed by extruding, molding or injection molding the TPU, the TPEE, the PEBAX, the TPU/PEBAX blend, the TPU/TPEE blend or the TPEE/PEBAX blend.
3. The process for preparing an ultra-light thermoplastic elastomer foam material as claimed in claim 1, wherein the saturation pressure, saturation temperature and saturation time in the first supercritical foaming are less than those of the second supercritical foaming.
4. The process for preparing an ultra-light thermoplastic elastomer foam material as claimed in claim 3, wherein the saturation temperature of the first supercritical foaming is 100 ℃ to 160 ℃, the saturation pressure is 7 Mpa to 10Mpa, and the saturation time is 0.5 h to 4 h; the saturation temperature of the second supercritical foaming is 120-170 ℃, the saturation pressure is 10-30Mpa, and the saturation time is 2-10 h.
5. The process for preparing the ultra-light thermoplastic elastomer foam material as claimed in claim 4, wherein the saturation temperature of the TPEE material carbon dioxide is 110-130 ℃, the saturation temperature of the TPU carbon dioxide is 140-160 ℃, the saturation temperature of the PEBAX carbon dioxide is 100-130 ℃, and the temperature range of the mixture is between the temperature ranges of the two mixtures.
6. The process for preparing the ultra-light thermoplastic elastomer foam material as claimed in claim 4, wherein the saturation temperature of TPEE nitrogen is 120-150 ℃, the saturation temperature of TPU nitrogen is 140-170 ℃, the saturation temperature of PEBAX nitrogen is 120-150 ℃, and the temperature range of the mixture is between the two temperature ranges.
7. The process for preparing an ultralight thermoplastic elastomer foam material according to claim 1, wherein the density of the foamed intermediate product is 0.3 to 0.5g/cm3。
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| CN202010406242.6A CN111718514A (en) | 2020-05-14 | 2020-05-14 | Preparation process of ultralight thermoplastic elastomer foam material |
| PCT/CN2021/079190 WO2021227613A1 (en) | 2020-05-14 | 2021-03-29 | Method for preparing ultra-light thermoplastic elastomer foaming material |
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Cited By (6)
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| WO2021227613A1 (en) * | 2020-05-14 | 2021-11-18 | 福建兴迅新材料科技有限公司 | Method for preparing ultra-light thermoplastic elastomer foaming material |
| CN114196168A (en) * | 2021-12-29 | 2022-03-18 | 安踏（中国）有限公司 | Preparation method of TPEE foamed sole |
| CN115216106A (en) * | 2022-02-21 | 2022-10-21 | 道一高分子聚合物(宁波)有限公司 | Preparation process of wear-resistant anti-skid novel supercritical foaming material |
| CN115260565A (en) * | 2022-08-15 | 2022-11-01 | 青岛科技大学 | TPEE foam and preparation process thereof |
| CN115850954A (en) * | 2022-11-22 | 2023-03-28 | 东莞海瑞斯新材料科技有限公司 | Supercritical foaming thermoplastic elastomer material and preparation method and application thereof |
| CN115975244A (en) * | 2022-12-27 | 2023-04-18 | 福建创合新材料科技有限公司 | Ultra-light elastic foam material and foaming process thereof |
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| CN115926237A (en) * | 2022-12-27 | 2023-04-07 | 福建创合新材料科技有限公司 | Foaming material and foaming process and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021227613A1 (en) * | 2020-05-14 | 2021-11-18 | 福建兴迅新材料科技有限公司 | Method for preparing ultra-light thermoplastic elastomer foaming material |
| CN114196168A (en) * | 2021-12-29 | 2022-03-18 | 安踏（中国）有限公司 | Preparation method of TPEE foamed sole |
| CN114196168B (en) * | 2021-12-29 | 2023-04-21 | 安踏（中国）有限公司 | Preparation method of TPEE foamed sole |
| CN115216106A (en) * | 2022-02-21 | 2022-10-21 | 道一高分子聚合物(宁波)有限公司 | Preparation process of wear-resistant anti-skid novel supercritical foaming material |
| CN115216106B (en) * | 2022-02-21 | 2023-09-22 | 道一高分子聚合物(宁波)有限公司 | Preparation process of novel wear-resistant and anti-skid supercritical foaming material |
| CN115260565A (en) * | 2022-08-15 | 2022-11-01 | 青岛科技大学 | TPEE foam and preparation process thereof |
| CN115850954A (en) * | 2022-11-22 | 2023-03-28 | 东莞海瑞斯新材料科技有限公司 | Supercritical foaming thermoplastic elastomer material and preparation method and application thereof |
| CN115975244A (en) * | 2022-12-27 | 2023-04-18 | 福建创合新材料科技有限公司 | Ultra-light elastic foam material and foaming process thereof |
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| WO2021227613A1 (en) | 2021-11-18 |
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