CN116655990A - Foaming method of thermoplastic elastomer and application thereof - Google Patents
Foaming method of thermoplastic elastomer and application thereof Download PDFInfo
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- CN116655990A CN116655990A CN202310627682.8A CN202310627682A CN116655990A CN 116655990 A CN116655990 A CN 116655990A CN 202310627682 A CN202310627682 A CN 202310627682A CN 116655990 A CN116655990 A CN 116655990A
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- 238000005187 foaming Methods 0.000 title claims abstract description 215
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 62
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000000463 material Substances 0.000 claims abstract description 59
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 49
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 49
- 239000003463 adsorbent Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 239000006260 foam Substances 0.000 claims abstract description 7
- 230000012010 growth Effects 0.000 claims abstract description 4
- 230000006911 nucleation Effects 0.000 claims abstract description 4
- 238000010899 nucleation Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 239000002808 molecular sieve Substances 0.000 claims description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 30
- 210000001161 mammalian embryo Anatomy 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 238000004090 dissolution Methods 0.000 claims description 17
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 12
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 12
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 210000000497 foam cell Anatomy 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 19
- 210000004027 cell Anatomy 0.000 description 11
- 238000000635 electron micrograph Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229920002614 Polyether block amide Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- 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
- C08J2323/02—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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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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
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a foaming method of a thermoplastic elastomer and application thereof, belonging to the technical field of foaming. The invention provides a foaming method of a thermoplastic elastomer, which comprises the following steps: blending a thermoplastic elastomer with a gas adsorbent to obtain a blend; molding the blend to obtain a foaming blank; and (3) physically foaming the foaming blank by taking carbon dioxide as a physical foaming agent to obtain the foaming material. According to the foaming method disclosed by the invention, the thermoplastic elastomer and the gas adsorbent are subjected to blending modification, the high adsorptivity of the gas adsorbent to carbon dioxide is utilized, the speed of the carbon dioxide escaping out of the foaming material is reduced, the pressure difference between gas in foam holes and the environment is reduced, the shrinkage problem of the foaming material is essentially solved, and meanwhile, the high adsorption quantity of the carbon dioxide in the gas adsorbent is utilized, so that the foaming material has higher foam hole nucleation capability and stronger foam hole growth driving force in the foaming process, and the foaming multiplying power of the foaming material is further improved.
Description
Technical Field
The invention relates to a foaming method of a thermoplastic elastomer and application thereof, belonging to the technical field of foaming.
Background
The thermoplastic elastomer has the excellent performances of high elasticity, ageing resistance and oil resistance of the traditional crosslinked vulcanized rubber, and has the characteristics of convenience in processing and wide processing mode of common plastics. The lightweight polymer foam material prepared by foaming the thermoplastic elastomer has wide application in the fields of aerospace, national defense, energy, traffic, packaging, electrical appliances, sports equipment and the like.
Physical foaming is a green foaming technology which uses supercritical fluid treated by carbon dioxide, nitrogen and other gases under high temperature and high pressure as a foaming agent. Among them, supercritical carbon dioxide is the most commonly used foaming agent in the field of physical foaming due to its high dissolution amount and strong bubble growth driving force. However, when a thermoplastic elastomer is physically foamed using supercritical carbon dioxide, the problem of shrinkage of the foamed material is remarkable. This is mainly because once the foamed material is formed, there is a tendency for the blowing agent to diffuse out of the cells and air to diffuse into the cells, whereas for foamed materials obtained by physically foaming thermoplastic elastomers with supercritical carbon dioxide, the diffusion rate of supercritical carbon dioxide in the thermoplastic elastomer is much higher than air (approximately 1 order of magnitude higher), the rapid escape of carbon dioxide causes a pressure drop in the cell structure, while the lower rigidity of the thermoplastic elastomer makes it difficult to support the cell structure under negative pressure, ultimately leading to shrinkage problems. The serious shrinkage not only can obviously increase the density of the foaming material, but also can cause obvious folds and depressions on the surface of the foaming material, thereby seriously affecting the subsequent use of the foaming material.
Currently, some studies have been attempted to solve the problem of shrinkage of a foamed material caused by physical foaming of a thermoplastic elastomer using supercritical carbon dioxide. For example, patent application publication No. CN111730794a discloses a supercritical fluid foaming method of a thermoplastic elastomer, which improves shrinkage problem of a foamed material by combining carbon dioxide and nitrogen blending foaming with pressure-variable saturation, but foaming magnification of the foamed material prepared by the method is still low (only 7 times after the foaming magnification of physical foaming is stabilized under the foaming pressure of 15MPa by using a thermoplastic polyurethane elastomer), and at the same time, pressure-variable saturation forms big and small pores inside the material, which affects uniformity of cell size. Therefore, it is needed to find a method capable of improving the shrinkage problem of the foaming material generated by physical foaming of the thermoplastic elastomer by using supercritical carbon dioxide and improving the foaming rate of the foaming material.
Disclosure of Invention
In order to solve the above-mentioned drawbacks, the present invention provides a foaming method of a thermoplastic elastomer, the foaming method comprising: blending a thermoplastic elastomer with a gas adsorbent to obtain a blend; molding the blend to obtain a foaming blank; and (3) physically foaming the foaming blank by taking carbon dioxide as a physical foaming agent to obtain the foaming material.
In one embodiment of the present invention, the gas adsorbent comprises one or more of activated carbon and molecular sieve; the molecular sieve comprises one or more of a carbon molecular sieve and a 13X type molecular sieve.
In one embodiment of the invention, the mass of the gas adsorbent in the blend is 0.5% to 10.0% of the total mass of the blend.
In one embodiment of the invention, the mass of the gas adsorbent in the blend is 1.0% to 5.0% of the total mass of the blend.
In one embodiment of the invention, the physical foaming is: placing the foaming embryo body in a foaming mold with the mold cavity temperature being the foaming temperature, and introducing carbon dioxide into the mold cavity until the pressure in the mold cavity reaches the foaming pressure; continuously placing the foaming embryo body in a die cavity with the pressure being the foaming pressure and the temperature being the foaming temperature until the carbon dioxide reaches dissolution balance in the foaming embryo body; and releasing the pressure in the die cavity to the ambient pressure at a pressure release rate, and inducing the nucleation and growth of the foam cells to enable the foaming blank to foam, so as to obtain the foaming material.
In one embodiment of the present invention, the foaming temperature is (Tm-50) DEG C to Tm DEG C, wherein Tm is the melting point of the thermoplastic elastomer.
In one embodiment of the present invention, the foaming pressure is 10 to 20MPa.
In one embodiment of the present invention, the foaming pressure is 13 to 18MPa.
In one embodiment of the invention, the pressure relief rate is 10 to 1000Mpa/s.
In one embodiment of the invention, the pressure relief rate is 100 to 500Mpa/s.
In one embodiment of the present invention, the thermoplastic elastomer comprises one or more of thermoplastic polyurethane elastomer (TPU), thermoplastic polyester elastomer (TPEE), nylon elastomer (PEBAX) and polyolefin elastomer (POE).
In one embodiment of the invention, when the thermoplastic elastomer comprises a polyolefin elastomer, the foaming process is: blending the thermoplastic elastomer, the gas adsorbent and the compatilizer to obtain a blend; molding the blend to obtain a foaming blank; and (3) physically foaming the foaming blank by taking carbon dioxide as a physical foaming agent to obtain the foaming material.
In one embodiment of the invention, the mass of the compatibilizer in the blend is 0.1 to 1.0 percent of the total mass of the blend.
In one embodiment of the invention, the mass of the compatibilizer in the blend is 0.3 to 0.8 percent of the total mass of the blend.
In one embodiment of the invention, the compatibilizing agent is a maleic anhydride graft of a polyolefin elastomer.
In one embodiment of the present invention, the foaming green body is in the form of beads, plates, sheets, rolls, or irregularities.
In one embodiment of the invention, the blending is performed using a twin screw extruder.
In one embodiment of the invention, the molding is hot press molding, extrusion molding or injection molding.
The invention also provides a foaming material, which is obtained by foaming by the foaming method.
The invention also provides application of the foaming method in preparing the foaming material.
The technical scheme of the invention has the following advantages:
the invention provides a foaming method of a thermoplastic elastomer, which comprises the following steps: blending a thermoplastic elastomer with a gas adsorbent to obtain a blend; molding the blend to obtain a foaming blank; and (3) physically foaming the foaming blank by taking carbon dioxide as a physical foaming agent to obtain the foaming material. According to the foaming method disclosed by the invention, the thermoplastic elastomer and the gas adsorbent are subjected to blending modification, and the high adsorptivity of the gas adsorbent to carbon dioxide is utilized to reduce the speed of the carbon dioxide escaping out of the foaming material, so that the pressure difference between gas in cells and the environment in the curing process of the elastomer foaming material is reduced, the shrinkage problem of the foaming material is essentially solved, and meanwhile, the high adsorptivity of the carbon dioxide in the gas adsorbent is utilized, so that the foaming material has higher cell nucleation capability and stronger cell growth driving force in the foaming process, and the foaming multiplying power of the foaming material is further improved, so that the foaming method has a great application prospect.
Further, the gas adsorbent is activated carbon or carbon molecular sieve. The activated carbon and the carbon molecular sieve still have stronger adsorptivity to carbon dioxide at higher temperature, and the physical foaming of the thermoplastic elastomer by using the activated carbon or the carbon molecular sieve as a gas adsorbent is beneficial to improving the shrinkage problem of the foaming material, and meanwhile, the foaming rate of the foaming material can be effectively improved.
Further, in the blend, the mass of the gas adsorbent accounts for 1.0-5.0% of the total mass of the blend. When the content of the gas adsorbent is low, the amount of carbon dioxide adsorbed is limited, and the expansion ratio is improved to a limited extent; when the content of the gas adsorbent is higher, agglomeration is easy to generate in the blend, foaming behavior is influenced, and moreover, as the gas adsorbent cannot foam, the excessive consumption can influence the foaming ratio of the foaming material and can influence the performance of the foaming material. The amount of the gas adsorbent can effectively improve the foaming ratio of the foaming material, and meanwhile, the rebound resilience and other performances of the foaming material are not affected.
Further, the foaming temperature of the physical foaming is (Tm-50) DEG C-Tm DEG C, wherein Tm is the melting point of the thermoplastic elastomer. If the foaming temperature is low, the strength of the thermoplastic elastomer is high, and cells are difficult to grow; if the foaming temperature is high, the thermoplastic elastomer has low strength, and it is difficult to support cells, resulting in failure of foaming. This foaming temperature aids in the foaming of the thermoplastic elastomer.
Further, when the thermoplastic elastomer comprises a polyolefin elastomer, the foaming method is: blending the thermoplastic elastomer, the gas adsorbent and the compatilizer to obtain a blend; molding the blend to obtain a foaming blank; performing physical foaming on the foaming blank by taking carbon dioxide as a physical foaming agent to obtain a foaming material; in the blend, the mass of the compatilizer accounts for 0.3-0.8% of the total mass of the blend. The polarity of the polyolefin elastomer is weaker, and the compatilizer can effectively improve the compatibility of the polyolefin elastomer and the gas adsorbent, thereby being beneficial to the foaming of the polyolefin elastomer.
Drawings
Fig. 1: electron microscopy images of the foamed product obtained in example 1.
Fig. 2: electron microscopy images of the foamed product obtained in example 2.
Fig. 3: electron microscopy images of the foamed product produced in example 3.
Fig. 4: electron microscopy images of the foamed product obtained in example 4.
Fig. 5: electron microscopy images of the foamed product obtained in example 5.
Fig. 6: electron microscopy images of the foamed product obtained in example 6.
Fig. 7: electron microscopy images of the foamed product prepared in comparative example 1.
Fig. 8: electron microscopy images of the foamed product prepared in comparative example 3.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The following examples do not identify specific experimental procedures or conditions, which may be followed by procedures or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The activated carbon (model ZHF) referred to in the following examples was purchased from Songxin Filter industry Co., ltd. In the consolidated market, the carbon molecular sieve (model CMS-200) was purchased from Ji Xin space division materials science Co., zhejiang, 13X-type molecular sieve was purchased from Shandong Yuan Lin Gui ceramic New Material Co., ltd., and the twin screw extruder (model SHJ-20) was purchased from Nanj Jenty electro-mechanical Co., ltd.).
Experimental example 1: influence of the selection of the gas adsorbent on the solubility of carbon dioxide in the thermoplastic elastomer
The experimental example provides an experiment for influencing the solubility of carbon dioxide in a thermoplastic elastomer by selecting a gas adsorbent, and the experimental process is as follows:
taking a gas-free adsorbent as a blank control, respectively blending and modifying TPU (1180A, BASF, tm=150℃) with three gas adsorbents of activated carbon, carbon molecular sieve and 13X-type molecular sieve in a mass ratio of 95:5 in a double screw extruder, extruding into a 10mm multiplied by 4mm foaming blank, weighing the foaming blank, and marking as m 1 The method comprises the steps of carrying out a first treatment on the surface of the Placing the foaming embryo in a high pressure die cavity (15 mm×15mm×6 mm), heating to 150deg.C, charging carbon dioxide into the high pressure die cavity to 15MPa, and maintaining the temperature and pressureUntil the carbon dioxide reaches dissolution balance in the foaming embryo; after reaching dissolution balance (taking 90 min), cooling the high-pressure die cavity to normal temperature (25 ℃), and then releasing the pressure of the high-pressure die cavity at a pressure release rate of 0.01MPa/s to obtain a foaming material, taking the foaming material out of the high-pressure die cavity, weighing, and marking as m 2 The method comprises the steps of carrying out a first treatment on the surface of the Price weighing results are put into the formulaTo calculate the solubility of carbon dioxide in the TPU, the results of the calculations are shown in table 1.
From the results in Table 1, it can be seen that the activated carbon and carbon molecular sieves still have strong adsorption of carbon dioxide at higher temperatures, while 13X type molecular sieves have little effect.
TABLE 1 solubility of carbon dioxide in TPU
| Gas adsorbent | Solubility of carbon dioxide |
| Activated carbon | 12.5％ |
| Carbon molecular sieve | 13.7％ |
| 13X type molecular sieve | 10.6％ |
| Blank control | 10％ |
Example 1: foaming method of thermoplastic elastomer
The embodiment provides a foaming method of a thermoplastic elastomer, which comprises the following steps: TPU (1180A, BASF, tm=150deg.C) and carbon molecular sieve are mixed and modified in a double screw extruder according to a mass ratio of 95:5, and then extruded into 10mm multiplied by 4mm foaming embryo; placing the foaming embryo body in a high-pressure die cavity (the size is 15mm multiplied by 6 mm), heating to 150 ℃ (foaming temperature), charging carbon dioxide into the high-pressure die cavity to 15MPa (foaming pressure), and keeping the temperature and the pressure until the carbon dioxide reaches dissolution balance in the foaming embryo body; after reaching dissolution equilibrium (taking 90 min), the pressure in the high-pressure die cavity is relieved at a pressure relief rate of 200MPa/s, and the foaming material is obtained.
Example 2: foaming method of thermoplastic elastomer
The embodiment provides a foaming method of a thermoplastic elastomer, which comprises the following steps: TPEE (4056, duPont, tm=150℃) and carbon molecular sieve are subjected to blending modification in a double screw extruder according to a mass ratio of 95:5, and then extruded into a 10mm multiplied by 4mm foaming embryo; placing the foaming embryo body in a high-pressure die cavity (the size is 15mm multiplied by 6 mm), heating to 145 ℃ (foaming temperature), charging carbon dioxide into the high-pressure die cavity to 15MPa (foaming pressure), and keeping the temperature and the pressure until the carbon dioxide reaches dissolution balance in the foaming embryo body; after reaching dissolution equilibrium (taking 90 min), the pressure in the high-pressure die cavity is relieved at a pressure relief rate of 200MPa/s, and the foaming material is obtained.
Example 3: foaming method of thermoplastic elastomer
The embodiment provides a foaming method of a thermoplastic elastomer, which comprises the following steps: PEBAX (4533, acomax, tm=147 ℃) and a carbon molecular sieve are subjected to blending modification in a double-screw extruder according to a mass ratio of 95:5, and then are extruded into a 10mm multiplied by 4mm foaming embryo; placing the foaming embryo body in a high-pressure die cavity (the size is 15mm multiplied by 6 mm), heating to 145 ℃ (foaming temperature), charging carbon dioxide into the high-pressure die cavity to 15MPa (foaming pressure), and keeping the temperature and the pressure until the carbon dioxide reaches dissolution balance in the foaming embryo body; after reaching dissolution equilibrium (taking 90 min), the pressure in the high-pressure die cavity is relieved at a pressure relief rate of 200MPa/s, and the foaming material is obtained.
Example 4: foaming method of thermoplastic elastomer
The embodiment provides a foaming method of a thermoplastic elastomer, which comprises the following steps: POE (EG 8450, dow chemical, tm=102℃), carbon molecular sieve and POE maleic anhydride graft (FB 521A, shanghai Jia Yi Rong) are subjected to blending modification in a double-screw extruder according to the mass ratio of 94.525:5:0.475, and then are extruded into 10mm multiplied by 4mm foaming embryo bodies; placing the foaming embryo body in a high-pressure die cavity (the size is 15mm multiplied by 6 mm), heating to 90 ℃ (foaming temperature), charging carbon dioxide into the high-pressure die cavity to 15MPa (foaming pressure), and keeping the temperature and the pressure until the carbon dioxide reaches dissolution balance in the foaming embryo body; after reaching dissolution equilibrium (taking 90 min), the pressure in the high-pressure die cavity is relieved at a pressure relief rate of 200MPa/s, and the foaming material is obtained.
Example 5: foaming method of thermoplastic elastomer
The embodiment provides a foaming method of a thermoplastic elastomer, which comprises the following steps: TPU (1180A, BASF, tm=150deg.C) and active carbon are subjected to blending modification in a double screw extruder according to a mass ratio of 95:5, and then are extruded into 10mm multiplied by 4mm foaming embryo bodies; placing the foaming embryo body in a high-pressure die cavity, heating to 150 ℃ (foaming temperature), charging carbon dioxide into the high-pressure die cavity (the size is 15mm multiplied by 6 mm) to 15MPa (foaming pressure), and keeping the temperature and the pressure until the carbon dioxide reaches dissolution balance in the foaming embryo body; after reaching dissolution equilibrium (taking 90 min), the pressure in the high-pressure die cavity is relieved at a pressure relief rate of 200MPa/s, and the foaming material is obtained.
Example 6: foaming method of thermoplastic elastomer
The embodiment provides a foaming method of a thermoplastic elastomer, which comprises the following steps: TPU (1180A, BASF, tm=150deg.C) and carbon molecular sieve are mixed and modified in a double screw extruder according to a mass ratio of 98:2, and then extruded into 10mm multiplied by 4mm foaming embryo; placing the foaming embryo body in a high-pressure die cavity (the size is 15mm multiplied by 6 mm), heating to 135 ℃ (foaming temperature), charging carbon dioxide into the high-pressure die cavity to 15MPa (foaming pressure), and keeping the temperature and the pressure until the carbon dioxide reaches dissolution balance in the foaming embryo body; after reaching dissolution equilibrium (taking 90 min), the pressure in the high-pressure die cavity is relieved at a pressure relief rate of 200MPa/s, and the foaming material is obtained.
Comparative example 1: foaming method of thermoplastic elastomer
This comparative example provides a foaming method of a thermoplastic elastomer, which removes carbon molecular sieve on the basis of example 1 to obtain a foamed material.
Comparative example 2: foaming method of thermoplastic elastomer
This comparative example provides a foaming method of a thermoplastic elastomer, which based on example 1, adjusts the mass ratio of TPU to carbon molecular sieve from 95:5 to 85:15 to obtain a foamed material.
Comparative example 3: foaming method of thermoplastic elastomer
This comparative example provides a foaming method of a thermoplastic elastomer, which is based on example 1, in which the foaming temperature is adjusted from 150 to 90℃to obtain a foamed material.
Comparative example 4: foaming method of thermoplastic elastomer
This comparative example provides a foaming method of a thermoplastic elastomer, which is based on example 1, wherein the foaming temperature is adjusted from 150 ℃ to 160 ℃ to obtain a foamed material.
Comparative example 5: foaming method of thermoplastic elastomer
This comparative example provides a foaming method of a thermoplastic elastomer, which replaces a carbon molecular sieve with a 13X type molecular sieve on the basis of example 1 to obtain a foamed material.
Experimental example 2: performance test of thermoplastic elastomer
The experimental example provides performance detection of the thermoplastic elastomer, and the experimental process is as follows:
the foaming materials prepared in examples 1 to 6 and comparative examples 1 to 5 were observed by a scanning electron microscope, and the obtained electron microscope images are shown in fig. 1 to 8. Reference is made to "Chen Y, li D, zhang H, ling Y, wu K, liu T, hu D, zhao l.antishrinking strategy of microcellular thermoplastic polyurethane by comprehensive modeling analysis.industrial & Engineering Chemistry research.2021apr 28;60 The foaming materials prepared in examples 1 to 5 and comparative examples 1 to 5 were examined for initial expansion ratio, stable post-expansion ratio and shrinkage ratio by the method described in 7155-66', and the examination results are shown in Table 2.
As can be seen from fig. 1 to 8 and table 2, examples 1 to 6 can prepare foaming materials with a larger foaming ratio, and the shrinkage rate of the obtained foaming materials is very low, which indicates that the two gas adsorbents of the carbon molecular sieve and the activated carbon play a positive role in the foaming process. Comparative example 1 was free of the gas adsorbent, so that shrinkage was very serious, up to 80% in spite of the higher initial foaming ratio; the gas adsorbent content of comparative example 2 was too high, resulting in a decrease in the overall foaming ratio; the foaming temperature of comparative example 3 is low, and cells are difficult to grow, so that the foaming ratio is low; the foaming temperature of comparative example 4 is too high, the cells are difficult to support, a large amount of cracks and collapse are generated, and thus the foaming ratio is low; comparative example 5 uses 13X type molecular sieve, which has a low carbon dioxide adsorption amount at high temperature, so improvement of shrinkage problem is limited, and shrinkage exceeds 40%.
TABLE 2 initial expansion ratio, stable post-expansion ratio and shrinkage ratio of foam
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A method of foaming a thermoplastic elastomer, the method comprising: blending a thermoplastic elastomer with a gas adsorbent to obtain a blend; molding the blend to obtain a foaming blank; and (3) physically foaming the foaming blank by taking carbon dioxide as a physical foaming agent to obtain the foaming material.
2. The foaming process of claim 1 wherein the gas adsorbent comprises one or more of activated carbon and molecular sieve; the molecular sieve comprises one or more of a carbon molecular sieve and a 13X type molecular sieve.
3. The foaming process of claim 1 or 2, wherein the mass of the gas adsorbent in the blend is from 0.5% to 10.0% of the total mass of the blend.
4. A foaming process according to any one of claims 1 to 3, wherein the mass of the gas adsorbent in the blend is from 1.0% to 5.0% of the total mass of the blend.
5. The foaming method according to any one of claims 1 to 4, wherein the physical foaming is: placing the foaming embryo body in a foaming mold with the mold cavity temperature being the foaming temperature, and introducing carbon dioxide into the mold cavity until the pressure in the mold cavity reaches the foaming pressure; continuously placing the foaming embryo body in a die cavity with the pressure being the foaming pressure and the temperature being the foaming temperature until the carbon dioxide reaches dissolution balance in the foaming embryo body; and releasing the pressure in the die cavity to the ambient pressure at a pressure release rate, and inducing the nucleation and growth of the foam cells to enable the foaming blank to foam, so as to obtain the foaming material.
6. The foaming method according to claim 5, wherein the foaming temperature is (Tm-50) DEG C to Tm DEG C, wherein Tm is the melting point of the thermoplastic elastomer.
7. The foaming method according to any one of claims 1 to 6, wherein the thermoplastic elastomer comprises one or more of a thermoplastic polyurethane elastomer, a thermoplastic polyester elastomer, a nylon elastomer and a polyolefin elastomer.
8. The foaming process of claim 7, wherein when the thermoplastic elastomer comprises a polyolefin elastomer, the foaming process is: blending the thermoplastic elastomer, the gas adsorbent and the compatilizer to obtain a blend; molding the blend to obtain a foaming blank; and (3) physically foaming the foaming blank by taking carbon dioxide as a physical foaming agent to obtain the foaming material.
9. A foamed material, characterized in that the foamed material is obtained by foaming by the foaming method according to any one of claims 1 to 8.
10. Use of the foaming process according to any of claims 1 to 8 for the preparation of a foamed material.
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| CN101033308A (en) * | 2006-12-22 | 2007-09-12 | 广东工业大学 | Method of preparing carrier foaming agent and application of the carrier foaming agent in polymer |
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| CN107177051A (en) * | 2017-06-05 | 2017-09-19 | 杭州博适特新材料科技有限公司 | The method for preparing thermoplastic elastomer foaming bead |
| CN112795091A (en) * | 2020-12-30 | 2021-05-14 | 苏州申赛新材料有限公司 | Foaming material and foaming product prepared from same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101033308A (en) * | 2006-12-22 | 2007-09-12 | 广东工业大学 | Method of preparing carrier foaming agent and application of the carrier foaming agent in polymer |
| CN105037930A (en) * | 2015-07-06 | 2015-11-11 | 安徽成方新材料科技有限公司 | Foamed polypropylene-high molecular absorbent composite material with uniform pore distribution, and preparation method thereof |
| CN107177051A (en) * | 2017-06-05 | 2017-09-19 | 杭州博适特新材料科技有限公司 | The method for preparing thermoplastic elastomer foaming bead |
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