CN114989570B - Crosslinked thermoplastic elastomer micro-foaming coiled material and preparation method and application thereof - Google Patents
Crosslinked thermoplastic elastomer micro-foaming coiled material and preparation method and application thereof Download PDFInfo
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- CN114989570B CN114989570B CN202210463299.9A CN202210463299A CN114989570B CN 114989570 B CN114989570 B CN 114989570B CN 202210463299 A CN202210463299 A CN 202210463299A CN 114989570 B CN114989570 B CN 114989570B
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 136
- 239000000463 material Substances 0.000 title claims abstract description 94
- 238000005187 foaming Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims description 18
- 229920001971 elastomer Polymers 0.000 claims description 17
- 239000000806 elastomer Substances 0.000 claims description 17
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 17
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002667 nucleating agent Substances 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 239000004677 Nylon Substances 0.000 claims description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 229920001778 nylon Polymers 0.000 claims description 5
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000002390 adhesive tape Substances 0.000 claims description 2
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000006260 foam Substances 0.000 abstract description 8
- 150000001298 alcohols Chemical class 0.000 abstract description 5
- 229920006037 cross link polymer Polymers 0.000 abstract description 5
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- 238000009826 distribution Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
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- 229920003020 cross-linked polyethylene Polymers 0.000 description 3
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229920006247 high-performance elastomer Polymers 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
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- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000013514 silicone foam Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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Abstract
The invention relates to the technical field of crosslinked polymer foamed coiled materials, in particular to a crosslinked thermoplastic elastomer micro-foamed coiled material and a preparation method and application thereof. The thickness of the crosslinked thermoplastic elastomer micro-foaming coiled material is 0.5-10 mm, and the density is 0.05-0.3 g/cm 3 The average cell size is 1-200 μm; the crosslinked thermoplastic elastomer micro-foamed coiled material comprises a thermoplastic elastomer, wherein the melting point of the thermoplastic elastomer is 150-200 ℃, and the crystallinity of the thermoplastic elastomer is 1-15%. The crosslinked thermoplastic elastomer micro-foamed coiled material has the advantages of uniform crosslinked network distribution, small and uniform foam hole size, low density, excellent heat resistance, good solvent resistance, smooth and clean surface crusting, controllable thickness and the like, has the thermal shrinkage rate of less than 2 percent at 110 ℃/1h, and can not generate obvious performance attenuation after being soaked in alcohols such as methanol, ethanol, butanol and the like for 1 h.
Description
Technical Field
The invention relates to the technical field of crosslinked polymer foamed coiled materials, in particular to a crosslinked thermoplastic elastomer micro-foamed coiled material and a preparation method and application thereof.
Background
The cross-linked polymer foamed coiled material comprises an electronic cross-linked polyethylene foamed coiled material, a cross-linked polyurethane foamed coiled material, a cross-linked organic silicon foamed coiled material and the like, has good flexibility, light weight and stretchability, has the functions of shock absorption, heat insulation, sound insulation and the like, and is applied to high-end fields of electronics, electric appliances, automobiles, sensing and the like. The electronic cross-linked polyethylene foaming coiled material is foamed by heating a chemical foaming agent pre-dispersed in a cross-linking system, and the density of the coiled material can be as low as 0.03g/cm 3 The foamed sheet of (2), however, the heat resistance of the foamed sheet product is generally lower than 100 ℃, and there are problems of poor elasticity and poor tensile recovery; the cross-linked polyurethane foam coiled material is prepared by adopting a reaction foaming method, and the foamed coiled material product has the problem of higher density; the crosslinked organosilicon foam coiled material can adopt chemical foamingThe foam is prepared by a reaction foaming method, has excellent heat resistance and good compression recovery performance, but has the problems of low tearing strength and large cell size. Meanwhile, it is difficult to prepare a crosslinked polyurethane foam coil and a crosslinked silicone foam coil having a density as low as 0.3g/cm 3 And a foamed roll having a thickness of less than 0.3 mm. Furthermore, the sizes of the foam holes of the cross-linked polymer foaming coiled material prepared by the prior art are all 200-500 microns, and are all more than 100-200 microns, and the heat insulation performance is poor. Therefore, there is a need in the industry to produce high performance crosslinked polymer microcellular foamed webs that are simultaneously microcellular, low density, high heat resistance, high thermal insulation, high tear, and high resilience.
The thermoplastic elastomer comprises thermoplastic polyurethane, thermoplastic polyester elastomer and thermoplastic nylon elastomer which are high-performance elastomers, the melting point of the thermoplastic elastomer is generally higher than 150 ℃, even can reach 200 ℃, the thermoplastic elastomer can meet a plurality of application requirements under the condition of no crosslinking, and meanwhile, the thermoplastic elastomer has the excellent characteristics of high resilience, high tear strength, high elastic recovery and the like. CN113248770A discloses a method for preparing a thermoplastic elastomer foamed coiled material by high-pressure fluid physical foaming, and the density of the prepared thermoplastic elastomer foamed coiled material is 0.1-0.6 g/cm 3 However, the density of the thermoplastic elastomer foamed coiled material can not reach the level of the electronic crosslinked polyethylene (can be as low as 0.03 to 0.05 g/cm) 3 ) Secondly, the thermoplastic elastomers have linear molecular structures and low crystallinity, and have poor solvent resistance, poor creep resistance and poor high-temperature thermal stability, which limits the application field of the thermoplastic elastomer foamed coiled materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a crosslinked thermoplastic elastomer micro-foaming coiled material, a preparation method and application thereof. The crosslinked thermoplastic elastomer micro-foamed coiled material has the advantages of uniform crosslinked network distribution, small and uniform foam hole size, low density, excellent heat resistance, good solvent resistance, smooth and clean surface crust, controllable thickness and the like, and the preparation conditions of the coiled material are mild, so that large-scale continuous production can be realized.
In order to realize the purpose, the invention adopts the technical scheme that:
the invention provides a crosslinked thermoplastic elastomer micro-foaming coiled material, wherein the thickness of the crosslinked thermoplastic elastomer micro-foaming coiled material is 0.5-10 mm, and the density of the crosslinked thermoplastic elastomer micro-foaming coiled material is 0.05-0.3 g/cm 3 The average cell size is 1-200 μm; the crosslinked thermoplastic elastomer micro-foaming coiled material comprises a thermoplastic elastomer, wherein the melting point of the thermoplastic elastomer is 150-200 ℃, and the crystallinity of the thermoplastic elastomer is 1-15%.
In the irradiation crosslinking process of the thermoplastic elastomer, molecular chains in an amorphous state are easy to crosslink, and molecular chains in a crystalline state are not easy to crosslink. Thermoplastic elastomers comprise a physically crosslinked network of crystalline ordered structures, which generally have a melting point higher than 150 ℃ and therefore have a high heat resistance, but the thermoplastic elastomers have a low crystallinity (e.g., 0 to 10%) and a linear molecular chain structure, which results in a thermoplastic elastomer foamed web having an insufficient heat resistance, poor solvent resistance and poor creep resistance.
The invention limits the melting point and the crystallinity of the thermoplastic elastomer, limits the molecular chain movement capacity of the thermoplastic elastomer melt, obtains the crosslinked thermoplastic elastomer with uniform crosslinked network structure after the thermoplastic elastomer is irradiated and crosslinked, and improves the thermal stability, the creep resistance and the chemical stability of the crosslinked thermoplastic elastomer.
The heat shrinkage rate of the crosslinked thermoplastic elastomer micro-foamed coiled material at 110 ℃/1h is less than 2%, and obvious performance attenuation can not occur after the coiled material is immersed in alcohols (alcohol resistance test) such as methanol, ethanol, butanol and the like for 1 h.
Preparing a foaming sample with the length and width larger than 10cm and 10cm, placing the foaming sample in an oven, taking out the foaming sample, measuring the length and width of the sample, and calculating the thermal shrinkage rate, wherein the formula is as follows: (initial length-post-shrinkage length)/initial length 100%.
As a preferred embodiment of the crosslinked thermoplastic elastomer micro-foamed web of the present invention, the crosslinked thermoplastic elastomer micro-foamed web comprises the following components in parts by weight:
80-100 parts of thermoplastic elastomer, 2-20 parts of polar elastomer, 0-3 parts of lubricant and 0-10 parts of nucleating agent.
As a preferred embodiment of the crosslinked thermoplastic elastomer micro-foamed web of the present invention, the thermoplastic elastomer comprises at least one of a thermoplastic polyurethane, a thermoplastic polyester elastomer, a nylon elastomer.
As a preferred embodiment of the crosslinked thermoplastic elastomer micro-foamed web of the present invention, the polar elastomer comprises an ethylene vinyl acetate copolymer or a polyolefin elastomer-maleic anhydride graft; the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 18-40 mol percent; the content of the maleic anhydride graft in the polyolefin elastomer maleic anhydride graft is 0.1-3.5 mol percent.
Preferably, the polyolefin elastomer-maleic anhydride graft comprises at least one of a maleic anhydride graft of ethylene vinyl acetate, a maleic anhydride graft of ethylene-propylene copolymer, and a maleic anhydride graft of ethylene-octene copolymer.
The ethylene-vinyl acetate copolymer or polyolefin elastomer-maleic anhydride graft has low density, good irradiation crosslinking capability and supercritical fluid foaming capability, and the addition of the ethylene-vinyl acetate copolymer or polyolefin elastomer-maleic anhydride graft can reduce the density of the crosslinked thermoplastic elastomer micro-foamed coiled material. Good compatibility is a prerequisite for the polar elastomer to improve the foaming properties of the crosslinked thermoplastic elastomer microcellular foamed webs.
The higher the vinyl acetate content of the ethylene vinyl acetate copolymer, the better its compatibility with the thermoplastic elastomer, but the lower the degree of radiation crosslinking of the elastomer composite; the higher the content of maleic anhydride grafts, the higher its compatibility with the thermoplastic elastomer, but it tends to cause the polar elastomer to exhibit a yellow and irritating taste, affecting the appearance and properties of the article. By limiting the content of vinyl acetate in the ethylene-vinyl acetate copolymer and the content of maleic anhydride grafts in the polyolefin elastomer-maleic anhydride grafts, the compatibility between the thermoplastic elastomer and the polar elastomer can be improved on the premise of not losing the performance of the elastomer composite.
As a preferred embodiment of the crosslinked thermoplastic elastomer micro-foamed web of the present invention, the gel content is from 10 to 60wt.%, preferably from 40 to 50wt.%. The gel content of the crosslinked thermoplastic elastomer was tested by the solvent extraction method.
According to the invention, the gel content in the crosslinked thermoplastic elastomer micro-foamed coiled material is limited to 10-60wt.%, when the gel content is higher than 60wt.%, the foam hole growth is hindered, the crosslinked thermoplastic elastomer micro-foamed coiled material with moderate expansion ratio is difficult to obtain, and when the gel content is lower than 10wt.%, the movement of a melt molecular chain is violent, the fluid viscosity is small, and the heat resistance and the chemical stability of the crosslinked thermoplastic elastomer micro-foamed coiled material can be influenced.
According to the invention, the gel content of the crosslinked thermoplastic elastomer is limited, and the crosslinked thermoplastic elastomer coiled material prepared by twin-screw extrusion casting film forming and irradiation crosslinking can meet the requirement of subsequent foaming.
Preferably, the lubricant is at least one of stearic acid, stearate and polyethylene wax; the nucleating agent is at least one of calcium carbonate, talcum powder, mica and montmorillonite, and the size of the nucleating agent is 0.3-10 microns.
The invention provides a preparation method of the crosslinked thermoplastic elastomer micro-foaming coiled material, which comprises the following steps:
1) Adding 80-100 parts of thermoplastic elastomer, 0-20 parts of polar elastomer, 0-3 parts of lubricant and 0-10 parts of nucleating agent into a double-screw casting machine, and performing extrusion casting film forming and irradiation crosslinking to obtain a crosslinked thermoplastic elastomer coiled material with a crosslinked structure;
(2) Placing the crosslinked thermoplastic elastomer web into supercritical N 2 Dipping in fluid to obtain a dipped and crosslinked thermoplastic elastomer coiled material, then carrying out low-temperature air-locking treatment on the dipped and crosslinked thermoplastic elastomer coiled material, and carrying out hot air temperature rise physical foaming to obtain a crosslinked thermoplastic elastomer micro-foaming coiled material.
As a preferred embodiment of the preparation method of the present invention, in the step (1), a twin-screw extruder is used for continuous extrusion and casting to obtain a thermoplastic elastomer film, wherein the material is dried by hot air, the moisture content after drying is less than 0.05%, the temperature from the feed inlet to the casting die head of the extruder is set to be 120/160/180/200/190/190 ℃, and the thickness of the casting film is 0.1-4.0 mm.
There is a "valley" type relationship between the foaming temperature of the impregnated thermoplastic elastomer web and the density of the foamed web, resulting in difficulty in continuing to reduce the density of the thermoplastic elastomer foamed web by increasing the foaming temperature after the density of the thermoplastic elastomer foamed web reaches a minimum value. The cross-linked structure improves the thermal stability of the foamed melt, thereby allowing the cell structure in the melt to be further increased, and further remarkably improving the supercritical fluid foaming behavior of the cross-linked thermoplastic elastomer micro-foamed coiled material.
Preferably, in the step (1), the irradiation crosslinking adopts at least one of an electron accelerator, a 60 Co-gamma ray source, a 137 Cs-gamma ray source, an X-ray and a neutron source; the irradiation dose for irradiation crosslinking is 10-200 kGy, preferably 20-160 kGy.
As a preferred embodiment of the preparation method of the present invention, in the step (2), supercritical N is used 2 The solubility of the fluid in the crosslinked thermoplastic elastomer micro-foamed web is between 0.1 and 3.0wt.%, preferably between 0.2 and 2.5wt.%.
As a preferable embodiment of the production method of the present invention, in the step (2), the density of the initially expanded micro-foamed web of the crosslinked thermoplastic elastomer after the physical foaming by heating with hot air is not less than 0.02g/cm 3 。
After the crosslinked thermoplastic elastomer is foamed by heating, the heated foaming agent in the foam hole can continuously escape, and air in the air cannot diffuse into the foam hole in time, so that the pressure difference can cause the crosslinked thermoplastic elastomer micro-foamed coiled material to shrink to a certain degree, uniform shrinkage can cause a smooth sample surface, uniform coiled material thickness and the like, and uneven shrinkage can cause wrinkles on the surface of the coiled material and uneven thickness. Generally, the shrinkage behavior of the foaming coiled material is influenced by the condition of initial expansion after temperature rise foaming, and the shrinkage behavior of the crosslinking thermoplastic elastomer foaming coiled material is controlled by limiting the density of the initial expansion coiled material after temperature rise foaming, wherein the density of the initial expansion coiled material refers to the density tested within 10min after the crosslinking thermoplastic elastomer micro-foaming coiled material is prepared.
In a third aspect, the present invention provides the use of the crosslinked thermoplastic elastomer micro-foamed web in chemical mechanical polishing, adhesive tape, electronic appliance, automobile, rail transit, wearable electronic consumer product, or shoe material.
Preferably, the crosslinked thermoplastic elastomer micro-foaming coiled material further comprises a foaming skin layer and an internal foaming core layer, and the size of cells in the foaming core layer is 1-200 mu m.
Supercritical N 2 The fluid has low gas diffusion rate, high cell nucleation capability and high utilization rate of the foaming agent. Supercritical N 2 Too low a fluid solubility will reduce the degree of expansion of the crosslinked thermoplastic elastomer micro-foamed web, while too high a fluid solubility will significantly increase the pressure of the supercritical fluid, resulting in a significant increase in equipment costs. By pairing N 2 The content of the fluid, the low-temperature air-locking temperature and the escape content of the foaming agent are limited, so that the stable foaming of the impregnated crosslinked thermoplastic elastomer coiled material is facilitated, and the crosslinked thermoplastic elastomer micro-foamed coiled material with low density, smooth surface and uniform thickness is obtained.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a crosslinked thermoplastic elastomer micro-foaming coiled material and a preparation method and application thereof, wherein the crosslinked thermoplastic elastomer coiled material with uniform crosslinking network and proper crosslinking content is prepared by selecting raw materials, designing a formula, extruding, casting and irradiating for crosslinking, and supercritical N is adopted 2 Fluid impregnation, low-temperature air locking treatment and heating foaming are carried out to prepare the crosslinked thermoplastic elastomer micro-foamed coiled material, and the method can realize large-scale continuous production, and is safe and environment-friendly. The invention limits the melting point and the crystallinity of the thermoplastic elastomer, limits the molecular chain movement capacity of the thermoplastic elastomer melt, obtains the crosslinked thermoplastic elastomer with uniform crosslinked network structure after the thermoplastic elastomer is irradiated and crosslinked, and improves the thermal stability and the resistance of the crosslinked thermoplastic elastomerCreep property and chemical stability, and then improve the stability of microfoaming coiled material, this microfoaming coiled material is suitable for and uses in a plurality of fields such as chemical mechanical polishing, sealed and shock attenuation of sticky tape, electron electrical apparatus, car, track traffic, wearable consumer electronics, buffer memory packing, shoes material.
Drawings
FIG. 1 is an optical photograph of a crosslinked thermoplastic elastomer micro-foamed web of the present invention;
FIG. 2 is a cell structure of a crosslinked thermoplastic elastomer micro-foamed web of the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
In the following examples and comparative examples, the experimental methods used were all conventional ones unless otherwise specified, and the materials, reagents and the like used were commercially available.
The materials used in the examples and comparative examples are as follows:
thermoplastic polyurethane 1 (TPU): melting point 150 deg.C, crystallinity 1%, model Texin 5270, germany Bayer.
Thermoplastic polyester elastomer 1 (TPEE): melting point 180 ℃ and crystallinity 10%, type 1028D, pasteur, germany.
Thermoplastic nylon elastomer 1 (TPAE-1): melting point 200 ℃ and crystallinity 15%, type 3010, asahu New Material science and technology, inc.
Thermoplastic nylon elastomer 2 (TPAE-2): melting point 180 deg.C, crystallinity 20%, model 4510, asahu New Material science and technology Limited.
Ethylene vinyl acetate copolymer 1: EVA, 28 mole fraction Vinyl Acetate (VA), model 265, du pont usa.
Ethylene vinyl acetate copolymer 2: EVA, vinyl Acetate (VA) content of 32 mole percent, type 750, japan Tosoh.
Ethylene vinyl acetate copolymer 3: EVA, vinyl Acetate (VA) content 40 mole percent, model 40W, duPont, USA.
Ethylene vinyl acetate copolymer 4: EVA, 18 mole fraction% Vinyl Acetate (VA), model 460, du pont usa.
Ethylene octene copolymer-maleic anhydride graft copolymer 1: POE, maleic anhydride graft (MA) content 0.5 mole percent, type N216, dow.
Ethylene octene copolymer-maleic anhydride graft copolymer 2: POE, maleic anhydride graft (MA) content 1.5 mole percent, model GR216, dow.
Ethylene octene copolymer-maleic anhydride graft copolymer 3: POE, maleic anhydride graft (MA) content 0.1 mole percent, type N493, dow.
Ethylene octene copolymer-maleic anhydride graft copolymer 4: POE, maleic anhydride graft (MA) content 3.5 mole percent, model GR208, dow.
Lubricant: stearic acid, commercially available.
Nucleating agent: calcium carbonate, with an average particle size of 1 micron, is commercially available.
The lubricants and nucleating agents in the examples and comparative examples were the same commercial products.
Examples 1 to 14
A preparation method of a crosslinked thermoplastic elastomer micro-foaming coiled material comprises the following steps:
1) Adding a thermoplastic elastomer, a polar elastomer, a lubricant and a nucleating agent into a twin-screw casting machine, continuously extruding and casting by using a twin-screw extruder to obtain a thermoplastic elastomer film, wherein the used material needs to be dried by hot air, the moisture content after drying is lower than 0.05 percent, the temperature from a feed inlet to a casting die head of the extruder is set to be 120/160/180/200/190/190 ℃, and then irradiating and crosslinking to obtain a crosslinked thermoplastic elastomer coiled material with a crosslinking structure;
(2) Placing the crosslinked thermoplastic elastomer web into supercritical N 2 Dipping in fluid to obtain dipped and crosslinked thermoplastic elastomer coiled material, then carrying out low-temperature air-locking treatment on the dipped and crosslinked thermoplastic elastomer coiled material, and carrying out hot air temperature rise physical foaming to obtain crosslinked thermoplastic elastomer coiled materialA thermoplastic elastomer microfoamed web.
FIG. 1 is an optical representation of a crosslinked thermoplastic elastomer micro-foamed web prepared in example 1, from which it can be seen that the foamed web has a smooth, flat surface and a uniform thickness. FIG. 2 is a diagram showing the structure of cells of a coil of a crosslinked thermoplastic elastomer microcellular foamed material prepared in example 1, wherein the cell size is small and the distribution of the cell structure is uniform. The specific formulation and preparation method of the crosslinked thermoplastic elastomer micro-foamed coiled material are shown in tables 1 and 2.
And (3) shrinkage testing: preparing a foaming sample with the length and width larger than 10cm and 10cm, placing the foaming sample in an oven, taking out the foaming sample, measuring the length and width of the sample, and calculating the thermal shrinkage rate, wherein the formula is as follows: (initial length-post-shrinkage length)/initial length 100%.
Alcohol resistance test: after being soaked in alcohols (such as methanol, ethanol, butanol and the like) for 1 hour, the performance of the composite material is not obviously attenuated to be good, and otherwise, the composite material is poor.
TABLE 1
TABLE 2
Example 17
Compared with the example 1, in the step 1), the materials are dried by hot air, the moisture content after drying is 0.1%, the surface of the foamed coiled material product has defects, and the inside of the foamed coiled material product has a large and small pore structure.
Comparative example 1
Compared with the example 1, the thermoplastic elastomer adopts TPAE-2 (crystallinity is 20%), the prepared crosslinked thermoplastic elastomer micro-foaming coiled material has uniform expansion and shrinkage on the surface, the product surface is smooth, the shrinkage rate at 110 ℃/1h is 8%, the alcohol resistance is poor, and obvious performance attenuation can not occur after the coiled material is soaked in alcohols such as methanol, ethanol, butanol and the like (alcohol resistance test) for 1 h.
Comparative example 2
Compared with the example 1, in the step 1), the crosslinking is not adopted, the thickness of the prepared crosslinked thermoplastic elastomer micro-foaming coiled material is 3.0, the density is 0.1, the cell size is 100 mu m, the foaming result shows that the foaming coiled material has higher shrinkage, the surface of the product has wrinkles, the shrinkage rate of the product at 110 ℃/1h is 20%, and the alcohol resistance is poor.
As can be seen from the data in tables 1-2, in examples 1-5, the gel content is 10-60wt.%, and the prepared crosslinked thermoplastic elastomer micro-foamed coiled material has uniform expansion and uniform shrinkage, smooth and clean product surface, small shrinkage at 110 ℃/1h, and no obvious performance attenuation after being soaked in alcohols such as methanol, ethanol, butanol and the like for 1 h.
The invention limits the melting point of the thermoplastic elastomer to be 150-200 ℃ and the crystallinity to be 1-15%, limits the molecular chain movement capacity of the thermoplastic elastomer melt, and improves the foaming uniformity of the crosslinked thermoplastic elastomer micro-foaming coiled material. Comparing example 10 with comparative example 1, the thermoplastic elastomer has crystallinity not within 1 to 15%, which has an effect on shrinkage of the crosslinked thermoplastic elastomer microcellular foamed web, and has poor alcohol resistance.
Examples 14-15, the prepared crosslinked thermoplastic elastomer microcellular foamed webs had uniform expansion and shrinkage, smooth surface, no shrinkage at 110 ℃/1 hour, and good alcohol resistance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. The crosslinked thermoplastic elastomer micro-foaming coiled material is characterized by having a thickness of 0.5-10 mm and a density of 0.05-0.3 g/cm 3 The average cell size is 1-200 μm; the crosslinked thermoplastic elastomer micro-foaming coiled material comprises a thermoplastic elastomer, wherein the melting point of the thermoplastic elastomer is 150-200 ℃, and the crystallinity of the thermoplastic elastomer is 1-15%;
the crosslinked thermoplastic elastomer micro-foaming coiled material comprises the following components in parts by weight:
80-100 parts of thermoplastic elastomer, 2-20 parts of polar elastomer, 0-3 parts of lubricant and 0-10 parts of nucleating agent;
the thermoplastic elastomer comprises at least one of thermoplastic polyurethane, thermoplastic polyester elastomer and nylon elastomer;
the polar elastomer comprises an ethylene vinyl acetate copolymer or a polyolefin elastomer-maleic anhydride graft; the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 18-40 mol percent; the content of the maleic anhydride graft in the polyolefin elastomer maleic anhydride graft is 0.1-3.5 mole percent; the gel content of the crosslinked thermoplastic elastomer micro-foaming coiled material is 10-60 wt.%;
the preparation method of the crosslinked thermoplastic elastomer micro-foaming coiled material comprises the following steps:
1) Adding 80-100 parts of thermoplastic elastomer, 2-20 parts of polar elastomer, 0-3 parts of lubricant and 0-10 parts of nucleating agent into a double-screw casting machine, and performing extrusion casting film forming and irradiation crosslinking to obtain a crosslinked thermoplastic elastomer coiled material with a crosslinked structure; wherein the materials are dried by hot air, and the moisture content after drying is lower than 0.05 percent;
(2) Placing the crosslinked thermoplastic elastomer web into supercritical N 2 Dipping in fluid to obtain a dipped and crosslinked thermoplastic elastomer coiled material, then carrying out low-temperature air-locking treatment on the dipped and crosslinked thermoplastic elastomer coiled material, and carrying out hot air temperature rise physical foaming to obtain a crosslinked thermoplastic elastomer micro-foaming coiled material.
2. The crosslinked thermoplastic elastomer microfoamed web of claim 1, wherein the crosslinked thermoplastic elastomer microfoamed web has a gel content of 40 to 50wt.%.
3. The web of crosslinked thermoplastic elastomer according to claim 1, wherein in the step (1), the thermoplastic elastomer film is obtained by continuous extrusion and casting using a twin-screw extruder, the temperature from the feed port to the casting die of the extruder is set to 120/160/180/200/190/190 ℃, and the thickness of the cast film is 0.1 to 4.0mm.
4. The web of crosslinked thermoplastic elastomer microfoamed material of claim 1 wherein in step (2), supercritical N 2 The solubility of the fluid in the crosslinked thermoplastic elastomer micro-foamed web is between 0.1 and 3.0wt.%.
5. The web of crosslinked thermoplastic elastomer microfoamed material of claim 4, wherein the supercritical N is 2 The solubility of the fluid in the crosslinked thermoplastic elastomer micro-foamed web is between 0.2 and 2.5wt.%.
6. The web of claim 1, wherein in step (2), the density of the initially expanded web of crosslinked thermoplastic elastomer after physical foaming at elevated temperature in hot air is not less than 0.02g/cm 3 。
7. Use of a crosslinked thermoplastic elastomer microfoamed web according to any of claims 1-6 in chemical mechanical polishing, adhesive tape, electronic, automotive, rail transit, wearable electronic consumer goods or footwear.
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