CN116444847A - Nylon elastomer foaming bead, preparation method and application thereof - Google Patents
Nylon elastomer foaming bead, preparation method and application thereof Download PDFInfo
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- CN116444847A CN116444847A CN202210008833.7A CN202210008833A CN116444847A CN 116444847 A CN116444847 A CN 116444847A CN 202210008833 A CN202210008833 A CN 202210008833A CN 116444847 A CN116444847 A CN 116444847A
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- nylon elastomer
- foaming
- agent
- nylon
- elastomer
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 219
- 239000000806 elastomer Substances 0.000 title claims abstract description 219
- 239000004677 Nylon Substances 0.000 title claims abstract description 208
- 229920001778 nylon Polymers 0.000 title claims abstract description 208
- 238000005187 foaming Methods 0.000 title claims abstract description 111
- 239000011324 bead Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000006260 foam Substances 0.000 claims abstract description 75
- 239000004088 foaming agent Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 29
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 27
- 239000002667 nucleating agent Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 tackifier Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 91
- 238000005520 cutting process Methods 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 13
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229920002292 Nylon 6 Polymers 0.000 claims description 10
- 239000004604 Blowing Agent Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920001610 polycaprolactone Polymers 0.000 claims description 9
- 239000004632 polycaprolactone Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 7
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 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 claims description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 5
- 229920006152 PA1010 Polymers 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 21
- 238000009826 distribution Methods 0.000 abstract description 8
- 238000004383 yellowing Methods 0.000 abstract description 8
- 238000009835 boiling Methods 0.000 abstract description 6
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- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 210000004027 cell Anatomy 0.000 description 34
- 238000007605 air drying Methods 0.000 description 11
- 230000003068 static effect Effects 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 10
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 210000000497 foam cell Anatomy 0.000 description 7
- 210000002421 cell wall Anatomy 0.000 description 6
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 description 5
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 description 3
- 241000948268 Meda Species 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005381 potential energy Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 2
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 241000482268 Zea mays subsp. mays Species 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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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
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
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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
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
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- 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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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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
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- 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
- C08J9/14—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 organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/12—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/011—Nanostructured additives
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- C08K3/041—Carbon nanotubes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a nylon elastomer foaming bead, a preparation method and application thereof, wherein the raw materials for forming the nylon elastomer foaming bead comprise the following components: nylon elastomer, tackifier, nucleating agent, antioxidant, foam homogenizing agent and physical foaming agent. The nylon elastomer foaming bead has stable performance and high processing efficiency, the problems of chemical degradation and yellowing of the nylon elastomer caused by long-time boiling water treatment are avoided, meanwhile, the nylon elastomer foaming bead has high melt strength, the crystallization performance requirement of a foaming process is met, and the obtained nylon elastomer foaming bead has the advantages of environmental friendliness, medium-high foaming multiplying power, excellent cell size distribution and good mechanical property. Therefore, the nylon elastomer foaming beads can be used in the fields of shoe materials, tires, ground coverings, indoor ornaments, sports equipment and the like.
Description
Technical Field
The invention belongs to the field of nylon materials, and particularly relates to a nylon elastomer foaming bead, a preparation method and application thereof.
Background
Thermoplastic elastomers are one of the fastest growing plastic varieties in the last 20 years, and nylon elastomers (TPAE) are a new thermoplastic elastomer being widely used, and were first commercialized by German corporation in 1979, and then subsequently commercialized by multiple companies in France, switzerland, japan, U.S.A. Nylon elastomers are of various types and are generally classified into nylon 6-based, nylon 66-based, nylon 12-based, and the like, depending on the type of polyamide constituting the hard segment.
Nylon elastomers (TPAE) are of relatively large variety, depending on the hard and soft segment composition. The vast majority of nylon elastomers currently on the market are polyether amide block copolymers (PEBA), small amounts of PEA (polyester block amide) and PEEA (polyether ester block amide). Compared with other thermoplastic elastomers (such as TPU, SBC, TPEE, etc.), the nylon elastomer has the advantages of good comprehensive performance, good processability, transparency, light weight, etc. The thermoplastic elastomer is a thermoplastic elastomer without plasticization, and the molecular chain has excellent flexibility, wide hardness range and good rebound resilience; the nylon elastomer material has good low-temperature shock resistance and is not hardened at low temperature; the hysteresis performance is low, and the dynamics performance is very good; is resistant to chemical corrosion, and has excellent anti-aging and sunlight exposure capability. Has good flex resistance and fatigue resistance, and can reduce fracture, increase rebound and have excellent hand feeling. Nylon elastomer materials are commonly used in the automotive industry, as shoe materials, as sports equipment, and the like.
At present, most of the preparation processes of nylon elastomer and the like in the market adopt kettle type supercritical foaming and steam molding. For example, the popcorn ETPU sole and the like also adopt similar production processes, the ETPU foaming multiplying power manufactured by the process is more than 10 times, various performances are excellent, and equipment and processes are relatively simple. However, the process is a discontinuous process, the preparation cost is high, the equipment is required to be subjected to special explosion-proof treatment, and the problems of low processing efficiency, unstable product performance batch and the like are also needed to be solved. Secondly, the nylon elastomer in the method relates to long-time boiling water treatment, which is easy to cause the problems of chemical degradation and yellowing of the nylon elastomer, and influences the performance and subsequent use of the elastomer foaming material.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present invention is to provide a nylon elastomer foaming bead, a preparation method and an application thereof, wherein the nylon elastomer foaming bead has stable performance, high processing efficiency, no problems of chemical degradation and yellowing of the nylon elastomer caused by long-time boiling water treatment, high melt strength of the nylon elastomer foaming bead, and meeting the crystallization performance requirements of a foaming process, and the obtained nylon elastomer foaming bead has the advantages of environmental friendliness, medium-high foaming multiplying power, excellent cell size distribution and good mechanical properties. Therefore, the nylon elastomer foaming beads can be used in the fields of shoe materials, tires, ground coverings, indoor ornaments, sports equipment and the like.
In one aspect of the invention, a nylon elastomer foam bead is provided. According to an embodiment of the present invention, the raw materials for forming the nylon elastomer foam beads include: nylon elastomer, tackifier, nucleating agent, antioxidant, foam homogenizing agent and physical foaming agent.
Therefore, the nylon elastomer foaming bead has stable performance and high processing efficiency, the problems of chemical degradation and yellowing of the nylon elastomer caused by long-time boiling water treatment are avoided, meanwhile, the nylon elastomer foaming bead has high melt strength, the crystallization performance requirement of a foaming process is met, and the obtained nylon elastomer foaming bead has the advantages of environmental friendliness, medium-high foaming multiplying power, excellent cell size distribution and good mechanical property. Therefore, the nylon elastomer foaming beads can be used in the fields of shoe materials, tires, ground coverings, indoor ornaments, sports equipment and the like.
In addition, the nylon elastomer foam beads according to the above embodiments of the present invention may have the following additional technical features:
in some embodiments of the invention, the mass ratio of the nylon elastomer, the tackifier, the nucleating agent, the antioxidant, and the foam homogenizing agent is 100: (0.5-2): (0.5-2): (0.5-1): (0.2-1). Thus, the nylon elastomer foaming beads with environmental friendliness, medium-high foaming multiplying power, excellent cell size distribution and good mechanical properties can be obtained.
In some embodiments of the invention, the nylon elastomer comprises polyamide elastomer hard segments comprising at least one of PA6, PA66, PA610, PA1010, PA1212, PA611, PA56, PA12, and PA612, and elastomer soft segments comprising at least one of tetrahydrofuran Polyether (PTMG), propylene oxide polyether (PPG), polyethylene glycol (PEG), polycaprolactone (PCL). Therefore, the obtained nylon elastomer foaming beads have the advantages of higher toughness and melt strength, uniform foam holes, smaller compressibility and high rebound resilience.
In some embodiments of the invention, the tackifier comprises at least one of pyromellitic anhydride PMDA, bulgerman M1251, MEDA (4, 4' -methylenebis (2, 6-diethylaniline), and a multifunctional epoxy (e.g., pasteur ADR4400, nanya NPES 909).
In some embodiments of the invention, the nucleating agent comprises at least one of nano-silica, montmorillonite, nano-zinc oxide whiskers, and carbon nanotubes. Thus, the higher-rate nylon elastomer foaming beads can be obtained later.
In some embodiments of the invention, the antioxidant includes at least one of antioxidant 1076, antioxidant O3, and antioxidant 1098.
In some embodiments of the invention, the foam homogenizing agent comprises at least one of AK8810, S-8123 and JSYK-500. Therefore, the surface tension of the nylon elastomer can be reduced, and the defects of foam cracking, closed pores and the like are eliminated.
In some embodiments of the invention, the injection pressure of the physical blowing agent is 5 to 20Mpa.
In some embodiments of the invention, the physical blowing agent comprises cyclopentane, n-butane, HFC-134a, and CO 2 At least one of them.
In some embodiments of the present invention, the physical blowing agent is used in an amount of 1.5 to 3 parts by weight based on 100 parts by weight of the nylon elastomer.
In a second aspect of the present invention, the present invention provides a process for preparing the nylon elastomer expanded beads described above. According to an embodiment of the invention, the method comprises:
(1) Mixing a nylon elastomer, a tackifier, a nucleating agent, an antioxidant and a foam homogenizing agent, and then carrying out melt blending to obtain a nylon elastomer blending system;
(2) Injecting a physical foaming agent into the nylon elastomer blending system and pressurizing to form a foaming agent/nylon elastomer homogeneous blending system;
(3) And (3) depressurizing and extruding the foaming agent/nylon elastomer homogeneous phase blending system to enable the foaming agent/nylon elastomer homogeneous phase blending system to be in a thermodynamically unstable state, driving cells to grow up, and then carrying out underwater circular cutting and drying to obtain nylon elastomer foaming beads.
According to the method for preparing the nylon elastomer foaming beads, the nylon elastomer, the tackifier and the finished product are preparedThe preparation method comprises the steps of mixing a nuclear agent, an antioxidant and a foam homogenizing agent, then carrying out melt blending, wherein the nuclear agent forms a large number of low potential energy points at interfaces among melts in the foaming process to form a large number of uniform nucleation hot spots, so that higher-magnification nylon elastomer foaming beads are obtained in the follow-up process, the adhesion promoter and the foam homogenizing agent cooperate to effectively improve the melt strength of the nylon elastomer and improve the foamability of the nylon elastomer, so that collapse, foam cell rupture and foam cell merging phenomena in the foaming process are prevented, meanwhile, the foam homogenizing agent and the nuclear agent cooperate to accelerate the foam forming speed in the nylon elastomer foaming beads, improve the mechanical property and the fineness of the foam beads, then inject the foam agent into a nylon elastomer blending system obtained by melt blending, then carry out pressurization, so that the physical foaming agent is dissolved in the nylon elastomer blending system to form a foam agent/nylon elastomer homogeneous blending system, finally, the obtained foam agent/nylon elastomer homogeneous blending system is subjected to depressurization and extrusion, so that the thermal foaming agent/nylon elastomer homogeneous blending is in an unstable state, the foam cell growth is driven, and the nylon elastomer foaming bead is obtained after the foam elastomer is cut into the nylon elastomer foaming beads after the ring and drying. Therefore, the method simplifies the foaming molding process of the nylon elastomer foaming beads, solves the problems of complex, poor continuity, unstable product performance and the like of the existing nylon elastomer kettle pressure foaming molding process, has stable performance, high processing efficiency and no problems of chemical degradation and yellowing of the nylon elastomer caused by long-time boiling water treatment, and meanwhile, the obtained nylon elastomer foaming beads have high melt strength, meet the crystallization performance requirement of the foaming process, and have the advantages of environmental friendliness, medium-high foaming multiplying power, excellent cell size distribution and good mechanical property. Specifically, the density of the nylon elastomer foaming beads obtained by the method is 80-200kg/m 3 The foaming multiplying power is 5-20 times, the size of the foam cells is 80-300um, and the difference between the maximum size and the minimum size of the foam cells is not more than 20 mu m. According to GB/T10652-2001 standard, the rebound rate of the foaming beads is more than or equal to 60%. According to GBT10799-2008 standard, the open cell content of the foaming beads is less than or equal to 10%; compressed form according to HG/T2876-2009 standardThe content of the active components is more than or equal to 30 percent. The expanded beads have a tensile strength of greater than 1.0MPa and an elongation at break of greater than or equal to 300% according to ASTM C297. Therefore, the nylon elastomer foaming beads can be used in the fields of shoe materials, tires, ground coverings, indoor ornaments, sports equipment and the like.
In addition, the method of preparing nylon elastomer foam beads according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the invention, in step (2), the injection pressure of the physical blowing agent is 10 to 30Mpa.
In some embodiments of the invention, in step (3), the water temperature of the underwater circular cutting is 50-80 ℃.
In some embodiments of the invention, the nylon elastomer expanded beads have a diameter of 0.5 to 1.5mm and a length of 1.5 to 3mm.
In a third aspect of the invention, the invention provides a foamed profile. According to the embodiment of the invention, the foaming special-shaped piece is prepared from the nylon elastomer foaming beads or the nylon elastomer foaming beads prepared by the method. Therefore, the foaming special-shaped piece has the advantages of environment friendliness, medium-high foaming multiplying power, excellent cell size distribution and good mechanical property, and can be used in the fields of shoe materials, tires, ground coverings, indoor ornaments, sports equipment and the like.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow diagram of a process for preparing nylon elastomer foam beads according to one embodiment of the invention;
FIG. 2 PA6 elastomer expanded beads obtained in example 1;
figure 3 SEM morphology of PA6 elastomer expanded beads obtained in example 1.
FIG. 4 example 2 gives a SEM profile of a cross section of a PA6/PETG expanded bead.
Detailed Description
The following detailed description of the embodiments of the invention is intended to be illustrative of the invention and is not to be taken as limiting the invention.
In one aspect of the invention, the invention provides a method of making nylon elastomer expanded beads. According to an embodiment of the present invention, the raw materials for forming the nylon elastomer foam beads include: nylon elastomer, tackifier, nucleating agent, antioxidant, foam homogenizing agent and physical foaming agent. The inventor finds that the nucleating agent forms a large number of low potential energy points at the interface between melts in the foaming process to form a large number of uniform nucleation hot spots, so that the subsequent obtaining of the nylon elastomer foaming beads with higher multiplying power is facilitated, the tackifier and the foam homogenizing agent cooperate to effectively improve the melt strength of the nylon elastomer and improve the foamability of the nylon elastomer, so that the phenomena of foam collapse, foam breaking and foam merging in the foaming process are prevented, and meanwhile, the foam homogenizing agent and the nucleating agent cooperate to accelerate the forming speed of foam in the nylon elastomer foaming beads, and the mechanical property and the fineness of the foam beads are improved.
Further, the mass ratio of the nylon elastomer, the tackifier, the nucleating agent, the antioxidant and the foam homogenizing agent is 100: (0.5-2): (0.5-2): (0.5-1): (0.2-1). The inventor finds that if the tackifier is added too high, the melt is gel-like, the melt is rough, the color is also deep, and the extrusion is not easy to carry out; if the tackifier is added too low, the foam cannot be supported to grow up, so that the foam collapse phenomenon is caused; if the addition of the nucleating agent is too much, agglomeration is formed, the formation of uniform cell structures is not facilitated, and if the addition of the nucleating agent is too low, an ideal nucleating effect is not obtained, heterogeneous nucleation points are few, and a compact foam structure cannot be formed; if the addition amount of the antioxidant is too high, the antioxidation stabilizing effect is not increased any more, and a precipitation phenomenon exists; if the antioxidant is added too low, the oxidability of the material cannot be effectively reduced, so that the material is discolored and degraded; if the addition amount of the foam homogenizing agent is too low, the corresponding functions of compatibilizing and regulating the cell structure cannot be achieved, and if the addition amount of the foam homogenizing agent is too high, the cells are finer, and even a closed cell phenomenon occurs. According to one embodiment of the present invention, the nylon elastomer includes a polyamide elastomer hard segment including at least one of PA6, PA66, PA610, PA1010, PA1212, PA611, and PA612, and an elastomer soft segment including at least one of tetrahydrofuran Polyether (PTMG), propylene oxide polyether (PPG), polyethylene glycol (PEG), polycaprolactone (PCL). The inventor also found that PETG has better viscosity, transparency, color, chemical resistance and stress whitening resistance, can be quickly thermoformed or extruded, has high transparency, excellent shock resistance, excellent processability and difficult yellowing of finished products. PETG is introduced into the nylon elastomer beads, the toughness and the melt strength of the foaming beads are higher, the foam cells are more uniform, and the rebound resilience is more excellent.
Further, the tackifier comprises at least one of pyromellitic anhydride PMDA, bulgmann M1251, MEDA (4, 4' -methylenebis (2, 6-diethylaniline) and multifunctional epoxy (such as BasfuADR 4400, nanya NPES 909), the nucleating agent comprises at least one of nano silicon dioxide, montmorillonite, nano zinc oxide whisker and carbon nano tube, the antioxidant comprises at least one of antioxidant 1076, antioxidant O3 and antioxidant 1098, the foam homogenizing agent is polysiloxane and comprises at least one of AK8810, S-8123 and JSYK-500, the inventor discovers that 1) the polysiloxane foam homogenizing agent has a molecular structure with oleophilicity and hydrophilicity, can emulsify foaming raw materials, improve the compatible state of the foaming materials before and after the blending reaction, and enable the foaming reaction and the tackifying reaction to smoothly proceed; 2) The existence of the polysiloxane foam homogenizing agent reduces the surface tension of the foaming raw material, the injected foaming gas is facilitated to enter the foam nucleus and continuously grow in the mixing process, and the polysiloxane foam homogenizing agent stabilizes thinned cell walls by reducing the stress in the cell walls in the foaming process until the cell walls have enough strength to prevent the rapidly-grown foam from collapsing; 3) The polysiloxane foam homogenizing agent eliminates the defects of foam cracking, closed pores and the like by reducing the surface tension of a nylon elastomer foaming system, so that the product is soft and elastic.
Further, according to the inventionIn one embodiment, the physical blowing agents include, but are not limited to, cyclopentane, n-butane, HFC-134a, and CO 2 At least one of (a) and (b); and the physical foaming agent is used in an amount of 1.5 to 3 parts by weight based on 100 parts by weight of the nylon elastomer. The inventor finds that if the addition amount of the foaming agent is too high, the excessive foaming agent does not participate in the process of growing up the cells because the solubility of the foaming agent in the nylon elastomer is limited, and perforation is easy to occur; if the addition amount of the physical foaming agent is too low, the foaming ratio is low, and the weight reduction is not obvious.
In a second aspect of the present invention, the present invention provides a process for preparing the nylon elastomer expanded beads described above. Referring to fig. 1, according to an embodiment of the present invention, the method includes:
s100: mixing nylon elastomer, tackifier, nucleater, antioxidant and foam homogenizing agent, and melt blending
In the step, the nylon elastomer, the tackifier, the nucleating agent, the antioxidant and the foam homogenizing agent are added into a ZE40 upper-stage double-screw extruder to be mixed and then are subjected to melt blending at 200-230 ℃ so as to obtain a nylon elastomer blending system. The inventor finds that the nucleating agent forms a large number of low potential energy points at the interface between melts in the foaming process to form a large number of uniform nucleation hot spots, so that the subsequent obtaining of the nylon elastomer foaming beads with higher multiplying power is facilitated, the tackifier and the foam homogenizing agent cooperate to effectively improve the melt strength of the nylon elastomer and improve the foamability of the nylon elastomer, so that the phenomena of foam collapse, foam breaking and foam merging in the foaming process are prevented, and meanwhile, the foam homogenizing agent and the nucleating agent cooperate to accelerate the forming speed of foam in the nylon elastomer foaming beads, and the mechanical property and the fineness of the foam beads are improved.
Further, the mass ratio of the nylon elastomer, the tackifier, the nucleating agent, the antioxidant and the foam homogenizing agent is 100: (0.5-2): (0.5-2): (0.5-1): (0.2-1). The inventor finds that if the tackifier is added too high, the melt is gel-like, the melt is rough, the color is also deep, and the extrusion is not easy to carry out; if the tackifier is added too low, the foam cannot be supported to grow up, so that the foam collapse phenomenon is caused; if the addition of the nucleating agent is too much, agglomeration is formed, the formation of uniform cell structures is not facilitated, and if the addition of the nucleating agent is too low, an ideal nucleating effect is not obtained, heterogeneous nucleation points are few, and a compact foam structure cannot be formed; if the addition amount of the antioxidant is too high, the antioxidation stabilizing effect is not increased any more, and a precipitation phenomenon exists; if the antioxidant is added too low, the oxidability of the material cannot be effectively reduced, so that the material is discolored and degraded; if the addition amount of the foam homogenizing agent is too low, the corresponding functions of compatibilizing and regulating the cell structure cannot be achieved, and if the addition amount of the foam homogenizing agent is too high, the cells are finer, and even a closed cell phenomenon occurs. According to one embodiment of the present invention, the nylon elastomer includes a polyamide elastomer hard segment including at least one of PA6, PA66, PA610, PA1010, PA1212, PA611, and PA612, and an elastomer soft segment including at least one of tetrahydrofuran Polyether (PTMG), propylene oxide polyether (PPG), polyethylene glycol (PEG), polycaprolactone (PCL). The inventor also found that PETG has better viscosity, transparency, color, chemical resistance and stress whitening resistance, can be quickly thermoformed or extruded, has high transparency, excellent shock resistance, excellent processability and difficult yellowing of finished products. PETG is introduced into the nylon elastomer beads, the toughness and the melt strength of the foaming beads are higher, the foam cells are more uniform, and the rebound resilience is more excellent.
Further, the tackifier comprises at least one of pyromellitic anhydride PMDA, bulgmann M1251, MEDA (4, 4' -methylenebis (2, 6-diethylaniline) and multifunctional epoxy (such as BasfuADR 4400, nanya NPES 909), the nucleating agent comprises at least one of nano silicon dioxide, montmorillonite, nano zinc oxide whisker and carbon nano tube, the antioxidant comprises at least one of antioxidant 1076, antioxidant O3 and antioxidant 1098, the foam homogenizing agent is polysiloxane and comprises at least one of AK8810, S-8123 and JSYK-500, the inventor discovers that 1) the polysiloxane foam homogenizing agent has a molecular structure with oleophilicity and hydrophilicity, can emulsify foaming raw materials, improve the compatible state of the foaming materials before and after the blending reaction, and enable the foaming reaction and the tackifying reaction to smoothly proceed; 2) The existence of the polysiloxane foam homogenizing agent reduces the surface tension of the foaming raw material, the injected foaming gas is facilitated to enter the foam nucleus and continuously grow in the mixing process, and the polysiloxane foam homogenizing agent stabilizes thinned cell walls by reducing the stress in the cell walls in the foaming process until the cell walls have enough strength to prevent the rapidly-grown foam from collapsing; 3) The polysiloxane foam homogenizing agent eliminates the defects of foam cracking, closed pores and the like by reducing the surface tension of a nylon elastomer foaming system, so that the product is soft and elastic.
S200: after physical foaming agent is injected into the nylon elastomer blending system, the temperature and the pressure of the single screw are reduced and increased
In this step, under certain gas injection pressure, a physical foaming agent is injected into the nylon elastomer blending system at the middle section of the ZE40 upper-stage twin-screw extruder, and the pressure is increased in the KE90 lower-stage single-screw extruder (the temperature is 190-220 ℃) to form a homogeneous foaming agent/nylon elastomer blending system in a static mixer. Preferably, the injection pressure of the physical foaming agent is 5 to 20Mpa, and the physical foaming agent is injected into the nylon elastomer blend system in the form of a supercritical fluid.
Further, according to one embodiment of the present invention, the physical blowing agents include, but are not limited to, cyclopentane, n-butane, HFC-134a, and CO 2 At least one of (a) and (b); and the physical foaming agent is used in an amount of 1.5 to 3 parts by weight based on 100 parts by weight of the nylon elastomer. The inventor finds that if the addition amount of the foaming agent is too high, the excessive foaming agent does not participate in the process of growing up the cells because the solubility of the foaming agent in the nylon elastomer is limited, and perforation is easy to occur; if the addition amount of the physical foaming agent is too low, the foaming ratio is low, and the weight reduction is not obvious.
S300: depressurizing and extruding a foaming agent/nylon elastomer homogeneous phase blending system
In the step, the obtained foaming agent/nylon elastomer homogeneous blend system is rapidly extruded by a porous die head in a depressurization way, so that the foaming agent/nylon elastomer homogeneous blend system is in a thermodynamically unstable state, the cells are driven to grow up, and then nylon elastomer foaming beads with the diameter of 0.5-1.5 mm and the length of 1.5-3 mm are obtained after underwater circular cutting (water temperature of 50-80 ℃) and drying (fluidized bed air drying).
The method simplifies the foaming molding process of the nylon elastomer foaming beads, solves the problems of complex, poor continuity, unstable product performance and the like of the existing nylon elastomer kettle pressure foaming molding process, has stable performance, high processing efficiency, does not have the problems of chemical degradation and yellowing of the nylon elastomer caused by long-time boiling water treatment, has high melt strength, meets the crystallization performance requirement of the foaming process, and has environmental friendliness, high and medium foaming multiplying power, excellent cell size distribution and good mechanical property. Specifically, the density of the nylon elastomer foaming beads obtained by the method is 80-200kg/m 3 The foaming multiplying power is 5-20 times, and the size of the foam holes is 80-300um. According to GB/T10652-2001 standard, the rebound rate of the foaming beads is more than or equal to 60%. According to GBT10799-2008 standard, the open cell content of the foaming beads is less than or equal to 10%; according to HG/T2876-2009 standard, compression set is not less than 30%. The expanded beads have a tensile strength of greater than 1.0MPa and an elongation at break of greater than or equal to 300% according to ASTM C297. Therefore, the nylon elastomer foaming beads can be used in the fields of shoe materials, tires, ground coverings, indoor ornaments, sports equipment and the like. It should be noted that the features and advantages described above for the nylon elastomer expanded beads are equally applicable to the method for preparing the nylon elastomer expanded beads, and are not described herein.
In a third aspect of the invention, the invention provides a foamed profile. According to the embodiment of the invention, the foaming special-shaped piece is prepared from the nylon elastomer foaming beads or the nylon elastomer foaming beads prepared by the method. Therefore, the foaming special-shaped piece has the advantages of environment friendliness, medium-high foaming multiplying power, excellent cell size distribution and good mechanical property, and can be used in the fields of shoe materials, tires, ground coverings, indoor ornaments, sports equipment and the like. It should be noted that the features and advantages described above for the nylon elastomer expanded beads and the preparation method thereof are also applicable to the expanded special-shaped member, and are not described herein.
The following detailed description of embodiments of the invention is provided for the purpose of illustration only and is not to be construed as limiting the invention. In addition, all reagents employed in the examples below are commercially available or may be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
(1) 100 parts by weight of TPAE (hard segment PA6, soft segment PTMG), 1 part by weight of Bulgerman M1251, 0.5 part by weight of nano silicon dioxide, 0.5 part by weight of antioxidant 1098 and 0.5 part by weight of AK-8810 (Jiangsu Meissun) are added into a ZE40 upper-stage twin-screw extruder, the temperature is set to 220 ℃, the rotating speed is set to 50rpm, and melt blending is carried out, so that a nylon elastomer blend system is obtained;
(2) 2 parts by weight of CO were fed into the middle section of a ZE40 upper stage twin-screw extruder at an injection pressure of 8MPa 2 Injecting a nylon elastomer blending system, pressurizing in a KE90 lower-stage single-screw extruder, setting the temperature to 210 ℃, setting the rotating speed to 10rpm, and forming a homogeneous foaming agent/nylon elastomer blending system in a static mixer;
(3) And (3) rapidly depressurizing and extruding the foaming agent/nylon elastomer blending system through a porous die head to enable the foaming agent/nylon elastomer homogeneous blending system to be in a thermodynamically unstable state, driving cells to grow up, and carrying out underwater circular cutting (water temperature 80 ℃) and fluidized bed air drying treatment to obtain nylon elastomer foaming beads with the diameter of 0.8mm and the length of 2mm, wherein photographs and SEM morphology diagrams are shown in figures 2 and 3.
Example 2
(1) 85 parts by weight of TPAE (hard segment PA6, soft segment PTMG), 15 parts by weight of PETG, 1 part by weight of Bulgerman M1251, 0.5 part by weight of nano silicon dioxide, 0.5 part by weight of antioxidant 1098 and 0.5 part by weight of AK-8810 (Jiangsu Maillard) are added into a ZE40 upper-stage double-screw extruder, the temperature is set to 220 ℃, the rotating speed is set to 50rpm, and melt blending is carried out, so that a nylon elastomer blend system is obtained;
(2) 2 parts by weight of CO were fed into the middle section of a ZE40 upper stage twin-screw extruder at an injection pressure of 8MPa 2 Injecting a nylon elastomer blending system, pressurizing in a KE90 lower-stage single-screw extruder, setting the temperature to 210 ℃, setting the rotating speed to 10rpm, and forming a homogeneous foaming agent/nylon elastomer blending system in a static mixer;
(3) The foaming agent/nylon elastomer blend system is rapidly extruded in a depressurization way through a porous die head, so that the foaming agent/nylon elastomer homogeneous blend system is in a thermodynamically unstable state, cells are driven to grow up, and nylon elastomer foaming beads with the diameter of 0.8mm and the length of 2mm are obtained through underwater circular cutting (water temperature of 80 ℃) and fluidized bed air drying treatment, wherein the cross section SEM is shown in figure 4.
Example 3
(1) 100 parts by weight of TPAE (hard segment PA66, soft segment PTMG), 1 part by weight of Bulgerman M1251, 0.5 part by weight of silicon dioxide and 0.8 part by weight of antioxidant O 3 Adding 0.5 part by weight of AK-8810 into a ZE40 upper-stage double-screw extruder, setting the temperature to 220 ℃ and the rotating speed to 50rpm for melt blending to obtain a nylon elastomer blending system;
(2) 2 parts by weight of CO were fed into the middle section of a ZE40 upper stage twin-screw extruder at an injection pressure of 8MPa 2 Injecting a nylon elastomer blending system, pressurizing in a KE90 lower-stage single-screw extruder, setting the temperature to 210 ℃, setting the rotating speed to 10rpm, and forming a homogeneous foaming agent/nylon elastomer blending system in a static mixer;
(3) And (3) rapidly depressurizing and extruding the foaming agent/nylon elastomer blending system through a porous die head to enable the foaming agent/nylon elastomer homogeneous blending system to be in a thermodynamically unstable state, driving cells to grow up, and carrying out underwater circular cutting (water temperature 80 ℃) and fluidized bed air drying treatment to obtain nylon elastomer foaming beads with the diameter of 1mm and the length of 2.0 mm.
Example 4
(1) Adding 100 parts by weight of nylon elastomer (hard segment PA610 and soft segment PTMG), 0.5 part by weight of PMDA, 2 parts by weight of montmorillonite, 0.5 part by weight of antioxidant 1098 and 0.2 part by weight of JSYK-500 (Jiangsu Jack) into a ZE40 upper-stage double-screw extruder, setting the temperature to 200 ℃ and setting the rotating speed to 50rpm for melt blending to obtain a nylon elastomer blending system;
(2) Under the gas injection pressure of 5MPa, 1.5 parts by weight of CO is added in the middle section of a ZE40 upper-stage double-screw extruder 2 Injecting a nylon elastomer blending system, pressurizing in a KE90 lower-stage single-screw extruder, setting the temperature to 190 ℃, setting the rotating speed to 10rpm, and forming a homogeneous foaming agent/nylon elastomer blending system in a static mixer;
(3) And (3) rapidly depressurizing and extruding the foaming agent/nylon elastomer blending system through a porous die head to enable the foaming agent/nylon elastomer homogeneous blending system to be in a thermodynamically unstable state, driving cells to grow up, and carrying out underwater circular cutting (water temperature 50 ℃) and fluidized bed air drying treatment to obtain nylon elastomer foaming beads with the diameter of 0.5mm and the length of 1.5 mm.
Example 5
(1) 100 parts by weight of nylon elastomer (hard segment PA1010, soft segment PPG), 0.5 part by weight of PMDA, 2 parts by weight of montmorillonite and 0.8 part by weight of antioxidant O 3 Adding 0.2 part by weight of JSYK-500 into a ZE40 upper-stage double-screw extruder, setting the temperature to 210 ℃ and the rotating speed to 50rpm for melt blending to obtain a nylon elastomer blending system;
(2) Injecting 1.8 parts by weight of HFC-134a into a nylon elastomer blending system in the middle section of a ZE40 upper-stage double-screw extruder under the gas injection pressure of 10MPa, pressurizing the mixture in a KE90 lower-stage single-screw extruder, setting the temperature to 200 ℃, setting the rotating speed to 10rpm, and forming a homogeneous foaming agent/nylon elastomer blending system in a static mixer;
(3) And (3) rapidly depressurizing and extruding the foaming agent/nylon elastomer blending system through a porous die head to enable the foaming agent/nylon elastomer homogeneous blending system to be in a thermodynamically unstable state, driving cells to grow up, and carrying out underwater circular cutting (water temperature 60 ℃) and fluidized bed air drying treatment to obtain nylon elastomer foaming beads with the diameter of 1.0mm and the length of 2 mm.
Example 6
(1) 100 parts by weight of nylon elastomer (hard segment PA1212, soft segment PPG), 2 parts by weight of MDEA, 1 part by weight of carbon nanotube, 0.8 part by weight of antioxidantAgent O 3 Adding 0.2 part by weight of JSYK-500 into a ZE40 upper-stage double-screw extruder, setting the temperature to 220 ℃ and setting the rotating speed to 50rpm for melt blending to obtain a nylon elastomer blending system;
(2) Injecting 1.8 parts by weight of HFC-134a into a nylon elastomer blending system in the middle section of a ZE40 upper-stage double-screw extruder under the air injection pressure of 15MPa, pressurizing the mixture in a KE90 lower-stage single-screw extruder, setting the temperature to 200 ℃, setting the rotating speed to 10rpm, and forming a homogeneous foaming agent/nylon elastomer blending system in a static mixer;
(3) And (3) rapidly depressurizing and extruding the foaming agent/nylon elastomer blending system through a porous die head to enable the foaming agent/nylon elastomer homogeneous blending system to be in a thermodynamically unstable state, driving cells to grow up, and carrying out underwater circular cutting (water temperature 70 ℃) and fluidized bed air drying treatment to obtain nylon elastomer foaming beads with the diameter of 1.5mm and the length of 2 mm.
Example 7
(1) 100 parts by weight of nylon elastomer (hard segment PA611, soft segment PEG), 2 parts by weight of MDEA, 1 part by weight of carbon nanotube and 0.8 part by weight of antioxidant O 3 Adding 1 part by weight of S-8123 (Van.C.) into a ZE40 upper-stage double-screw extruder, setting the temperature to 230 ℃ and the rotating speed to 50rpm for melt blending to obtain a nylon elastomer blending system;
(2) 2.2 parts by weight of cyclopentane is injected into a nylon elastomer blending system in the middle section of a ZE40 upper-stage double-screw extruder under the gas injection pressure of 9MPa, the pressure is increased in a KE90 lower-stage single-screw extruder, the temperature is set to 210 ℃, the rotating speed is set to 10rpm, and a homogeneous foaming agent/nylon elastomer blending system is formed in a static mixer;
(3) And (3) rapidly depressurizing and extruding the foaming agent/nylon elastomer blending system through a porous die head to enable the foaming agent/nylon elastomer homogeneous blending system to be in a thermodynamically unstable state, driving cells to grow up, and carrying out underwater circular cutting (water temperature 80 ℃) and fluidized bed air drying treatment to obtain nylon elastomer foaming beads with the diameter of 1.5mm and the length of 3mm.
Example 8
(1) Adding 100 parts by weight of nylon elastomer (hard segment PA612 and soft segment PEG), 1 part by weight of Basoff ADR4400, 0.5 part by weight of nano zinc oxide whisker, 1 part by weight of antioxidant 1076 and 1 part by weight of S-8123 into a ZE40 upper-stage double-screw extruder, and carrying out melt blending at the temperature of 225 ℃ and the rotating speed of 50rpm to obtain a nylon elastomer blending system;
(2) 2 parts by weight of cyclopentane is injected into a nylon elastomer blending system in the middle section of a ZE40 upper-stage double-screw extruder under the gas injection pressure of 7MPa, the pressure is increased in a KE90 lower-stage single-screw extruder, the temperature is set to 220 ℃, the rotating speed is set to 10rpm, and a homogeneous foaming agent/nylon elastomer blending system is formed in a static mixer;
(3) And (3) rapidly depressurizing and extruding the foaming agent/nylon elastomer blending system through a porous die head to enable the foaming agent/nylon elastomer homogeneous blending system to be in a thermodynamically unstable state, driving cells to grow up, and carrying out underwater circular cutting (water temperature 65 ℃) and fluidized bed air drying treatment to obtain nylon elastomer foaming beads with the diameter of 0.8mm and the length of 2 mm.
Example 9
(1) Adding 100 parts by weight of nylon elastomer (hard segment PA56 and soft segment PCL), 1 part by weight of ADR4400, 0.5 part by weight of nano zinc oxide whisker, 1 part by weight of antioxidant 1076 and 1 part by weight of S-8123 into a ZE40 upper-stage twin-screw extruder, and carrying out melt blending at the temperature of 215 ℃ and the rotating speed of 50rpm to obtain a nylon elastomer blending system;
(2) Injecting 3 parts by weight of n-butane into a nylon elastomer blending system in the middle section of a ZE40 upper-stage double-screw extruder under the gas injection pressure of 12MPa, pressurizing the nylon elastomer blending system in a KE90 lower-stage single-screw extruder, setting the temperature to 215 ℃, setting the rotating speed to 10rpm, and forming a homogeneous foaming agent/nylon elastomer blending system in a static mixer;
(3) And (3) rapidly depressurizing and extruding the foaming agent/nylon elastomer blending system through a porous die head to enable the foaming agent/nylon elastomer homogeneous blending system to be in a thermodynamically unstable state, driving cells to grow up, and carrying out underwater circular cutting (water temperature is 75 ℃) and fluidized bed air drying treatment to obtain nylon elastomer foaming beads with the diameter of 0.8mm and the length of 2 mm.
Example 10
(1) Adding 100 parts by weight of nylon elastomer (hard segment PA12 and soft segment PCL), 1 part by weight of Basoff NPES909, 0.5 part by weight of nano zinc oxide whisker, 0.5 part by weight of antioxidant 1098 and 1 part by weight of S-8123 into a ZE40 upper-stage double-screw extruder, and carrying out melt blending at 205 ℃ and 50rpm to obtain a nylon elastomer blending system;
(2) 2 parts by weight of CO were fed into the middle section of a ZE40 upper stage twin-screw extruder at an injection pressure of 8MPa 2 Injecting a nylon elastomer blending system, pressurizing in a KE90 lower-stage single-screw extruder, setting the temperature to 205 ℃, setting the rotating speed to 10rpm, and forming a homogeneous foaming agent/nylon elastomer blending system in a static mixer;
(3) And (3) rapidly depressurizing and extruding the foaming agent/nylon elastomer blending system through a porous die head to enable the foaming agent/nylon elastomer homogeneous blending system to be in a thermodynamically unstable state, driving cells to grow up, and carrying out underwater circular cutting (water temperature 78 ℃) and fluidized bed air drying treatment to obtain nylon elastomer foaming beads with the diameter of 1mm and the length of 2 mm.
Evaluation:
1. the nylon elastomer expanded beads obtained in examples 1 to 10 were evaluated for density, expansion ratio, cell size, rebound resilience, open cell content, compression set, tensile strength and elongation at break;
2. method for evaluating properties of polyester elastomer expanded beads:
foam density: according to GB/T6343-86
Foaming ratio: ratio of density of material after foaming to density before foaming
Cell size: scanning Electron Microscope (SEM) sizing
Rebound rate: according to GB/T10652-2001 standard
Opening ratio: according to GBT10799-2008 standard
Compression set: according to HG/T2876-2009 standard
Tensile strength and elongation at break: according to ASTM C297 standard
The results of the nylon elastomer foam beads obtained in examples 1 to 10 are shown in Table 1.
TABLE 1 data on the performance of the nylon elastomer expanded beads obtained in examples 1 to 10
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (12)
1. A nylon elastomer foam bead characterized in that the raw materials forming the nylon elastomer foam bead comprise: nylon elastomer, tackifier, nucleating agent, antioxidant, foam homogenizing agent and physical foaming agent.
2. The expanded bead according to claim 1, wherein the mass ratio of the nylon elastomer, the tackifier, the nucleating agent, the antioxidant and the foam homogenizing agent is 100: (0.5-2): (0.5-2): (0.5-1): (0.2-1).
3. The expanded bead of claim 1 or 2, wherein the nylon elastomer comprises polyamide elastomer hard segments comprising at least one of PA6, PA66, PA610, PA1010, PA1212, PA611, PA56, PA12, and PA612, and elastomer soft segments comprising at least one of tetrahydrofuran polyether, propylene oxide polyether, polyethylene glycol, and polycaprolactone.
4. The expanded beads according to claim 1 or 2, wherein the tackifier comprises at least one of pyromellitic anhydride, bragg mann M1251, 4' -methylenebis (2, 6-diethylaniline), and multifunctional epoxies;
optionally, the nucleating agent comprises at least one of nano silica, montmorillonite, nano zinc oxide whisker and carbon nanotube;
optionally, the antioxidants include at least one of antioxidant 1076, antioxidant O3, and antioxidant 1098;
optionally, the foam homogenizing agent comprises at least one of AK8810, S-8123 and JSYK-500.
5. The expanded beads according to claim 1, wherein the injection pressure of the physical blowing agent is 5 to 20MPa.
6. The expanded beads of claim 1 or 5, wherein the physical blowing agent comprises cyclopentane, n-butane, HFC-134a, and CO 2 At least one of them.
7. The expanded bead according to claim 6, wherein the physical blowing agent is used in an amount of 1.5 to 3 parts by weight based on 100 parts by weight of the nylon elastomer.
8. A method of making the nylon elastomer expanded beads of any one of claims 1-7, comprising:
(1) Mixing a nylon elastomer, a tackifier, a nucleating agent, an antioxidant and a foam homogenizing agent, and adding the mixture into a double-screw extruder for melt blending so as to obtain a nylon elastomer blending system;
(2) After the physical foaming agent is injected into the nylon elastomer blending system, the temperature is reduced through a single screw extruder, and the melt pressure is increased, so that a foaming agent/nylon elastomer homogeneous blending system is formed;
(3) And (3) depressurizing and extruding the foaming agent/nylon elastomer homogeneous phase blending system to enable the foaming agent/nylon elastomer homogeneous phase blending system to be in a thermodynamically unstable state, driving cells to grow up, and then carrying out underwater circular cutting and drying to obtain nylon elastomer foaming beads.
9. The method according to claim 8, wherein in step (2), the melt pressure is 10 to 30MPa.
10. The method according to claim 8, wherein in the step (3), the water temperature of the underwater circular cutting is 50 to 80 ℃.
11. The method of claim 8, wherein the nylon elastomer expanded beads have a diameter of 0.5 to 1.5mm and a length of 1.5 to 3mm.
12. A foamed profile, characterized in that it is produced from the nylon elastomer foamed beads according to any one of claims 1 to 7 or produced by the method according to any one of claims 8 to 11.
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| CN119219915A (en) * | 2024-11-28 | 2024-12-31 | 万华化学集团股份有限公司 | A nylon elastomer, a nylon elastomer foam material, and a preparation method and application thereof |
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| CN113755017A (en) * | 2018-10-23 | 2021-12-07 | 安踏（中国）有限公司 | Foam material for shoes, preparation method and application thereof |
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