CN112646325A - TPEE-material foamed shoe insole material and preparation process thereof - Google Patents
TPEE-material foamed shoe insole material and preparation process thereof Download PDFInfo
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- CN112646325A CN112646325A CN202011547328.7A CN202011547328A CN112646325A CN 112646325 A CN112646325 A CN 112646325A CN 202011547328 A CN202011547328 A CN 202011547328A CN 112646325 A CN112646325 A CN 112646325A
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- Prior art keywords
- tpee
- foaming
- thermoplastic polyester
- parts
- foamed
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- 239000000463 material Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims abstract description 87
- 238000005187 foaming Methods 0.000 claims abstract description 63
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002667 nucleating agent Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- 239000012530 fluid Substances 0.000 claims description 21
- 238000002347 injection Methods 0.000 claims description 18
- 239000007924 injection Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 17
- 229920001169 thermoplastic Polymers 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000004416 thermosoftening plastic Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 238000007493 shaping process Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- -1 2, 4-di-tert-butylphenyl Chemical group 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 241001133184 Colletotrichum agaves Species 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 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 3
- 230000003068 static effect Effects 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 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 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims 2
- 229910052623 talc Inorganic materials 0.000 claims 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 abstract description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 230000000711 cancerogenic effect Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 231100000315 carcinogenic Toxicity 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000009967 tasteless effect Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 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 9
- 239000000203 mixture Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 210000000497 foam cell Anatomy 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 238000013012 foaming technology Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000386 athletic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
-
- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/0095—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
- 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
- C08J9/141—Hydrocarbons
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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
- C08J9/14—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
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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
- C08J9/14—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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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
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- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K13/02—Organic and inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/52—Phosphorus bound to oxygen only
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- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Molding Of Porous Articles (AREA)
Abstract
The invention relates to the technical field of shoe material foamed midsoles, in particular to a foamed shoe midsole material made of TPEE (thermoplastic polyurethane elastomer) and a preparation process thereof. The TPEE material foaming insole material comprises the following raw materials: thermoplastic polyester elastomer, foaming agent, nucleating agent, antioxidant, lubricant, crosslinking agent and cell stabilizer. The invention has the following advantages: compared with the most common EVA foaming insole, the thermoplastic polyester elastomer foaming material has excellent fatigue resistance, and the insole made of the thermoplastic polyester elastomer foaming material can still keep softness, shock absorption performance and rebound resilience for a long time after being repeatedly trodden; the TPEE foaming material adopted by the invention has excellent temperature resistance, and compared with a TPU foaming insole, the thermoplastic polyester elastomer foaming material has the advantages of lower density after foaming than TPU, light weight, high rebound rate and strong weather resistance; the invention is non-toxic and tasteless, and has good recycling property. The production process does not produce any harmful carcinogenic substances. The method is in line with low-carbon, environment-friendly and green manufacturing, and can be recycled and developed sustainably.
Description
Technical Field
The invention relates to the technical field of shoe material foamed midsoles, in particular to a foamed shoe midsole material made of TPEE material and a preparation process thereof.
Background
The midsole is the core technology of a pair of shoes, and is also the core mark of various manufacturers, standing on the basis. To a shoes material insole material, bradyseism, kick-back, soft, light, five durable characteristics are crucial, however common EVA and PU foaming insole on the market at present not only hardly compromise above-mentioned five characteristics, EVA insole itself resistance to pressure is poor, often warp easily after the multiple compression and difficult kick-back leads to the durability poor, and PU insole material density itself is big, even be limited by the technique behind the foaming and often not lighter enough, and the sole foaming technique adopts the chemical foaming technique on the market at present, this foaming technique can degrade the accessory substance and remain in the foaming material, can cause harm to environment and human body. In addition, the EVA and PU foaming insole adopts a bridging agent, belongs to a thermosetting material and cannot be recycled.
At present, most of ultralight high-elastic foamed shoe materials still use EVA, POE, EPDM and the like as main bodies, but when the insole of the foamed shoe material is impacted by external force for a long time, the resilience and the fatigue resistance of the insole still need to be improved. Therefore, various manufacturers need a novel shoe material foaming insole material which can meet five characteristics of shoe materials, accords with the concept of sustainable development, has high resilience and fatigue resistance, and needs to be upgraded in other comprehensive properties to meet market demands.
Thermoplastic polyester elastomer (TPEE) is a block copolymer comprising hard polyester segments and soft polyether segments, the soft polyether segments and the amorphous polyester forming amorphous phase hard polyester segments partially crystallized to form crystalline domains serving as physical crosslinking sites. The foaming material is free from introducing a cross-linking agent, is environment-friendly and nontoxic, has excellent elasticity of rubber and easy processability of thermoplastic plastics, and is widely applied to shoe materials in recent years. However, TPEE is easy to generate macropores, open pores or uneven pore diameters during foaming due to low melt strength, so that no TPEE midsole invention product exists in the domestic market at present.
Therefore, the technical work in the field focuses on developing a lighter, high-resilience and fatigue-resistant foamed midsole material which is unique in the market and is made of environment-friendly TPEE material.
Disclosure of Invention
In view of the above defects in the prior art, the technical problem to be solved by the invention is to provide a novel midsole foam material formula with better performance, a foaming agent and an extrusion foaming technology with more advanced and environment-friendly performance, a TPEE material foam shoe midsole material with good rebound performance of products, and a preparation process thereof.
In order to achieve the purpose, the invention provides a foaming shoe midsole material made of TPEE, which comprises the following raw materials: 80-100 parts of thermoplastic polyester elastomer, 1-10 parts of foaming agent, 1.2-4 parts of nucleating agent, 0.1-3 parts of antioxidant, 1-5 parts of lubricant, 0.5-3 parts of crosslinking agent and 0.2-2 parts of foam stabilizer.
Furthermore, the Shore D hardness of the thermoplastic polyester elastomer is 25-60, and the density is 1.10-1.39 g/cm3；
Further, the supercritical fluid foaming agent is one or a mixture of carbon dioxide, nitrogen, isobutane, isopentane, hexane, heptane and fluorine-containing gas;
further, a material which contributes to the maintenance of foaming of the thermoplastic elastomer raw material, such as an azo compound, fluorine-free propane, a hydrocarbon blowing agent, and a heat-expandable microcapsule, may be selected, and the content of the material added is preferably 1 to 5% of the total mass of the corresponding thermoplastic polyester elastomer raw material; more preferably, the heat-expandable microcapsule raw material may be selected from one or more of Sakaif-190D, Sakai FN-105, available from Sakai corporation;
further, the nucleating agent is one or more of talcum powder, calcium carbonate, montmorillonite and white carbon black;
further, the antioxidant is one or more of antioxidant 168, antioxidant 1076, antioxidant 1098 and antioxidant 1010;
further, the lubricant is one or a mixture of wax powder, non-polar PE wax, talcum powder, oligomeric stearate and zinc stearate;
further, the crosslinking agent is one or more of dicumyl peroxide (DCP), tert-butyl cumyl peroxide (TBCP), dibenzoyl peroxide (BPO) and di-tert-butyl cumyl peroxide (BIPB).
Further, the cell stabilizer is one or more of acrylic compounds.
According to the foaming shoe midsole material made of the TPEE material, the invention provides a related manufacturing process, which comprises the following steps:
(1) drying before feeding: putting the TPEE particles into a vacuum drying oven to be dried for 3 hours at the temperature of 80 ℃;
(2) storing materials, primary melting: after the raw materials are dried, the raw materials enter a machine barrel through a weightlessness type limited precise feeding machine, heating, shearing and plasticizing are carried out on the front section of a screw rod of a double-extruder, and after the raw materials enter a metering section and are uniformly plasticized, primary melting TPEE molten gel is formed;
(3) injecting supercritical foaming gas: pressurizing a supercritical fluid by a high-pressure pump, injecting the pressurized supercritical fluid into the thermoplastic polyester elastic melt in the cylinder at a constant flow rate through the control of a metering valve, mixing for the first time, and mixing the thermoplastic polyester/supercritical fluid two-phase system into a liquid homogeneous system through a mixing element at the head of a screw and a static mixer;
(4) secondary plasticization: the gas-saturated homogeneous phase liquid TPEE system enters a single screw to be plasticized for the second time, so that the gas-saturated homogeneous phase TPEE system becomes a supersaturated system and forms a large number of micropore gas nuclei;
(5) injection molding: injecting the prepared TPEE foaming body by using a special-shaped intercepting type porous injection nozzle by adopting a special injection process, injecting the prepared TPEE foaming body into a female die below in a foaming strip mode, moving the female die back and forth at a speed until the female die is stacked and filled with foaming materials, and then closing the male die up and down for hot press molding;
(6) cooling and shaping: after the forming process is finished, the pressure in the cavity is reduced to enable the bubbles to expand, meanwhile, the cooling effect of the mold enables the bubbles to be solidified and shaped, and after the forming process is finished, the mold is opened and is demoulded to finish the foaming shoe insole made of TPEE material.
Compared with the shoe material insole material on the market, the invention has the following advantages:
1. compared with the most common EVA foaming insole, the thermoplastic polyester elastomer foaming material has excellent fatigue resistance, and the insole made of the thermoplastic polyester elastomer foaming material can still keep softness, cushioning performance and rebound resilience for a long time after being repeatedly trodden.
2. Compared with the TPU foaming insole, the thermoplastic polyester elastomer foaming material has the advantages that the density is lower than that of the TPU after foaming, the weight is light, the rebound rate is 5-15% higher than that of the TPU, the weather resistance is high, and the TPU is not easy to yellow, so that not only is the actual running of a runner more labor-saving, but also the primary color can be kept on the appearance of the insole.
3. The invention is different from the traditional foaming material, adopts the novel green supercritical fluid foaming technology of the foaming gas, is nontoxic and tasteless, and has good recycling property. The production process does not produce any harmful carcinogenic substances. The method is in line with low-carbon, environment-friendly and green manufacturing, and can be recycled and developed sustainably.
4. The TPEE foaming material adopted by the invention has excellent temperature resistance, can be suitable for a temperature range as high as 70 ℃, particularly has stable micro-pore structure after long-term high temperature, does not generate permanent retraction as common foaming materials, and shows excellent size stability. In addition, the excellent low-temperature performance is as low as-40 ℃, so that the hardening and even the brittle fracture of the middle sole of the running shoe in extreme weather can be avoided, and the running shoe is endowed with excellent and constant foot feeling and performance at low temperature.
Drawings
FIG. 1 is a flow chart of a manufacturing process of a foamed midsole material made of TPEE according to the present invention.
Detailed Description
To facilitate an understanding of the teachings of the present invention, reference will now be made to the following descriptions taken in conjunction with the accompanying drawings, in which some embodiments are described in greater detail below with reference to athletic footwear. For example, some embodiments described herein may be applicable to sports requiring lateral movement, such as tennis, basketball, soccer, badminton, and the like. It is emphasized, however, that the present invention is not limited to these embodiments with respect to such fact. Conversely, the invention may also be applied, for example, to shoes for longitudinal and lateral movements, such as basketball shoes, golf shoes, football shoes, climbing or dancing shoes, as well as to other kinds of sports shoes or for traditional walking shoes, etc.
Furthermore, many technical embodiments, several of which are described in more detail below, are conceivable as embodiments of the present invention. However, the present invention is not limited to the embodiments specifically described herein.
The foamed shoe insole material made of the TPEE material comprises the following raw materials in parts by weight: 80-100 parts of thermoplastic polyester elastomer, 1.2-4 parts of nucleating agent, 1-10 parts of foaming agent, 0.1-3 parts of antioxidant, 0.2-2 parts of foam stabilizer, 1-5 parts of lubricant and 0.5-3 parts of crosslinking agent.
In the TPEE foamed shoe midsole material, the adopted test standard of the thermoplastic polyester elastomer raw material is international standard ISO868, and the Shore hardness is 25-60D; the test standard is ISO1183, and the measured density is 1.10-1.39 g/cm3The domestic brand of the foaming agent and the safe and nontoxic supercritical foaming fluid provided for the national brand are beneficial to greatly reducing the residual stress of the product after foaming, reducing deformation and improving the dimensional stability. The nucleating agent is preferably talcum powder, the density of foam cells is improved when the nucleating agent is introduced for foaming, the foam cells are closed spheres, the size of the foam cells is reduced, the distribution tends to be uniform, independent closed foam cells are formed, and the effect of obviously closing the foam cells is achievedThe density of the product is reduced. The antioxidant is preferably 168 or 1010, the thermoplastic elastomer has general defects and is easy to yellow, and the TPEE material is also degraded under the action of ultraviolet light, so that the antioxidant and yellowing-resistant agent needs to be introduced into the formula. The lubricant is preferably wax powder or talcum powder, and on one hand, the introduction of the talcum powder not only has the function of enabling the TPEE material to be higher in foaming nucleation, but also enables the whole system to be faster and uniform in dispersion, and a stable homogeneous system is better formed in pre-foaming. The cell stabilizer is preferably a conventional acrylic product on the market; the cross-linking using the peroxide cross-linking agent can not only generate chemical bonds between linear molecules and connect the linear molecules with each other to form a net structure, which helps to improve the elasticity and strength of the TPEE, but also helps to form fine and uniform cells of the TPEE foam material and simultaneously improves the heat resistance and weather resistance of the product. Preferably, the density of the product obtained is between 0.220 and 0.280g/cm, measured according to the international test standard ISO11833The rebound resilience is 60-80% tested according to the Chinese standard GB/T6670-2008.
A TPEE material foamed shoe midsole material comprises the following preparation steps:
(1) drying before feeding: putting the TPEE particles into a vacuum drying oven to be dried for 3 hours at the temperature of 80 ℃;
(2) storing materials, primary melting: after the raw materials are dried, the raw materials enter a machine barrel through a weightlessness type limited precise feeding machine, heating, shearing and plasticizing are carried out on the front section of a screw rod of a double-extruder, and after the raw materials enter a metering section and are uniformly plasticized, primary melting TPEE molten gel is formed;
(3) injecting supercritical foaming gas: pressurizing a supercritical fluid by a high-pressure pump, injecting the pressurized supercritical fluid into the thermoplastic polyester elastic melt in the cylinder at a constant flow rate through the control of a metering valve, mixing for the first time, and mixing the thermoplastic polyester/supercritical fluid two-phase system into a liquid homogeneous system through a mixing element at the head of a screw and a static mixer;
(4) secondary plasticization: the gas-saturated homogeneous phase liquid TPEE system enters a single screw to be plasticized for the second time, so that the gas-saturated homogeneous phase TPEE system becomes a supersaturated system and forms a large number of micropore gas nuclei;
(5) injection molding: injecting the prepared TPEE foaming body by using a special-shaped intercepting type porous injection nozzle by adopting a special injection process, injecting the prepared TPEE foaming body into a female die below in a foaming strip mode, moving the female die back and forth at a speed until the female die is stacked and filled with foaming materials, and then closing the male die up and down for hot press molding;
(6) cooling and shaping: after the forming process is finished, the pressure in the cavity is reduced to enable the bubbles to expand, meanwhile, the cooling effect of the mold enables the bubbles to be solidified and shaped, and after the forming process is finished, the mold is opened and is demoulded to finish the foaming shoe insole made of TPEE material.
Example 1
The invention discloses a TPEE material foamed shoe midsole material, which comprises the following steps:
preparing raw materials: 85 parts of thermoplastic polyester elastomer, 3.4 parts of talcum powder, 0.4 part of cell stabilizer, 1.0 part of DCP and the use names and parts of the rest auxiliary agents are shown in Table 1.
TABLE 1 examples use the names and parts of raw materials
Drying TPEE particles in a vacuum drying box at 80 ℃ for 3 hours, uniformly mixing the TPEE particles with an auxiliary agent, and then passing the mixture through a weightless type precise feeding machine at a constant speed of 120cm3The method comprises the following steps of (1) blanking, plasticizing materials by a double-screw extruder, carrying out preliminary melting and mixing on a feeding section and a compression section, injecting a supercritical fluid into a foaming machine to form a thermoplastic polyester/supercritical fluid two-phase system when the materials enter a metering section under the condition that the pressure value is 8kpa, and then, shearing and plasticizing again to form a saturated two-phase system in the metering section; cooling and secondarily plasticizing the homogeneous system in a single-screw extruder to form a supersaturated two-phase system, continuously forming a large amount of microporous gas nuclei to form a thermoplastic polyester elastomer foaming state, and performing injection molding to obtain the thermoplastic polyester with a storage pressure of 50kpa, an injection pressure of 80kpa and an injection speed of 55cm by using a special-shaped interception type porous nozzle3The technological parameters of 220 deg.c/s, 6s injection time are filled into specific mold, and the setting temperature is controlledAnd (3) setting at 50 ℃ for 300s, automatically demolding the formed and processed product, and finishing the middle sole of the TPEE shoe material with a large amount of uniform micropore structures to obtain the product performance indexes of different embodiments shown in the table 2.
TABLE 2 product Performance indices
Example 2
The invention discloses a TPEE material foamed shoe midsole material, which comprises the following steps:
preparing raw materials: 95 parts of thermoplastic polyester elastomer, 1.2 parts of talcum powder serving as a lubricant, 2 parts of a mixture of talcum powder and wax powder serving as a nucleating agent, 1 part of a cell stabilizer, 1.2 parts of a mixture of DCP and BPO, and the use names and the parts of the rest auxiliaries are shown in Table 3.
TABLE 3 example use name and parts of raw materials
Drying TPEE particles in a vacuum drying box at 90 ℃ for 2 hours, uniformly mixing the TPEE particles with an auxiliary agent, and then passing the mixture through a weightless type precise feeding machine at a constant speed of 150cm3The method comprises the following steps of (1) blanking, plasticizing materials by a double-screw extruder, carrying out preliminary melting and mixing on a feeding section and a compression section, injecting a supercritical fluid into a foaming machine to form a thermoplastic polyester/supercritical fluid two-phase system when the materials enter a metering section under the condition that the pressure value is 6kpa, and then, shearing and plasticizing again to form a saturated two-phase system in the metering section; cooling and secondarily plasticizing the homogeneous system in a single-screw extruder to form a supersaturated two-phase system, continuously forming a large amount of microporous gas nuclei to form a thermoplastic polyester elastomer foaming state, and performing injection molding to obtain the thermoplastic polyester with a storage pressure of 60kpa, an injection pressure of 85kpa and an injection speed of 45cm by using a special-shaped interception type porous nozzle3Filling the specific mold with technological parameters of 210 deg.c/s, 210 deg.c and 8s material injecting time, setting temperature of 40 deg.c and settingThe molding time is 360 seconds, the product is automatically demoulded after the molding processing is finished, and the middle sole of the TPEE shoe material with a large amount of uniform micropore structures is finished, so that the product performance indexes of different embodiments shown in the table 4 are obtained.
TABLE 4 product Performance index
Example 3
The invention discloses a TPEE material foamed shoe midsole material, which comprises the following steps:
preparing raw materials: the thermoplastic polyester elastomer 100 parts, the lubricant 2.2 parts of nonpolar PE wax, the nucleating agent 3 parts of wax powder, the cell stabilizer 2 parts, BIPB2 parts, and the use names and parts of the rest auxiliaries are shown in Table 5.
TABLE 5 examples use the names and parts of raw materials
Drying TPEE particles in a vacuum drying box at 80 ℃ for 2 hours, uniformly mixing the TPEE particles with an auxiliary agent, and then passing the mixture through a weightless type precise feeding machine at a constant speed of 150cm3The method comprises the following steps of (1) blanking, plasticizing materials by a double-screw extruder, carrying out preliminary melting and mixing on a feeding section and a compression section, injecting a supercritical fluid into a foaming machine to form a thermoplastic polyester/supercritical fluid two-phase system when the materials enter a metering section under the condition that the pressure value is 8kpa, and then, shearing and plasticizing again to form a saturated two-phase system in the metering section; cooling and secondarily plasticizing the homogeneous system in a single-screw extruder to form a supersaturated two-phase system, continuously forming a large amount of microporous gas nuclei to form a thermoplastic polyester elastomer foaming state, and performing injection molding to obtain the thermoplastic polyester with a storage pressure of 70kpa, an injection pressure of 90kpa and an injection speed of 45cm by using a special-shaped interception type porous nozzle3The process parameters of the temperature of the injection nozzle is 200 ℃ and the injection time is 10s are filled in a specific mould, the shaping temperature is controlled at 40 ℃, the shaping time is 300s, and the product is shaped and processed automaticallyAnd (4) performing dynamic demolding to finish the TPEE shoe material midsole with a large amount of uniform micropore structures, and obtaining the product performance indexes of different embodiments shown in the table 6.
TABLE 6 product Performance index
Example 4
The invention discloses a TPEE material foamed shoe midsole material, which comprises the following steps:
preparing raw materials: 95 parts of thermoplastic polyester elastomer, 2.2 parts of talcum powder serving as a lubricant, 3 parts of wax powder serving as a nucleating agent, 1.5 parts of foam stabilizer, 1.5 parts of BIPB, and the use names and parts of the rest auxiliaries are shown in Table 7.
TABLE 7 EXAMPLES use names and raw material parts
Drying TPEE particles in a vacuum drying box at 80 ℃ for 2 hours, uniformly mixing the TPEE particles with an auxiliary agent, and then passing the mixture through a weightless type precise feeding machine at a constant speed of 100cm3The method comprises the following steps of (1) blanking, plasticizing materials by a double-screw extruder, carrying out preliminary melting and mixing on a feeding section and a compression section, injecting a supercritical fluid into a foaming machine to form a thermoplastic polyester/supercritical fluid two-phase system when the materials enter a metering section under the condition that the pressure value is 9kpa, and then, shearing and plasticizing again to form a saturated two-phase system in the metering section; cooling and secondarily plasticizing the homogeneous system in a single-screw extruder to form a supersaturated two-phase system, continuously forming a large amount of microporous gas nuclei to form a thermoplastic polyester elastomer foaming state, and performing injection molding to obtain the thermoplastic polyester with a storage pressure of 80kpa, an injection pressure of 80kpa and an injection speed of 60cm by using a special-shaped interception type porous nozzle3The technological parameters of the temperature of the nozzle is 200 ℃ and the material injection time is 10s are filled in a specific mould, the shaping temperature is controlled at 45 ℃, the shaping time is 240s, the product is automatically demoulded after the shaping processing is finished, and the product with a large number of uniform micropore structures is finishedThe product performance indexes of different embodiments of the TPEE shoe material midsole shown in the table 8 are obtained.
TABLE 8 product Performance index
In the embodiment, the adopted test standard of the density of the foamed sole is the Chinese chemical industry standard HG/T2872-2009; the hardness detection method is used for detecting according to the national standard GB/T10807-2006; the detection method of the compression deformation rate is carried out according to the national standard GB/T6669-2008; the rebound rate detection method is used for detecting according to the national standard GB/T6670-2008; the light color fastness detection method is used for detecting according to DB 35/T1691-; the detection method of the damping performance G value is carried out according to the national standard GB/T30907-.
In the different arrangements or assemblies illustrated in the figures and described above, components and steps not shown or described are still possible. Similarly, some features and subcombinations are of utility and may be employed without reference to other features and subcombinations. The examples of the present invention are for illustrative purposes and not to limit the invention, and alternative examples will be apparent to the reader of this patent. The invention is therefore not limited to the description above or in the drawings, but various embodiments and modifications do not depart from the scope of the appended claims.
Claims (10)
1. The foamed shoe midsole material made of the TPEE material is characterized by comprising the following raw materials in parts by weight: 80-100 parts of thermoplastic polyester elastomer, 1-10 parts of foaming agent, 1.2-4 parts of nucleating agent, 0.1-3 parts of antioxidant, 1-5 parts of lubricant, 0.5-3 parts of crosslinking agent and 0.2-2 parts of foam stabilizer.
2. The foamed midsole material of TPEE according to claim 1, wherein the thermoplastic polyester elastomer has a shore hardness of 25-60D.
3. The TPEE foamed midsole material as claimed in claim 1, wherein the thermoplastic polyester elastomer has a density of 1.10 to 1.39g/cm3。
4. The foamed shoe midsole material of TPEE material as claimed in claim 5, wherein said gas foaming agent is a supercritical fluid comprising one or more of carbon dioxide, nitrogen, isobutane, isopentane, hexane, heptane, fluorine-containing gas.
5. The TPEE foamed midsole material of claim 1, wherein the nucleating agent is one or more of talc, calcium carbonate, montmorillonite, and silica.
6. The TPEE foamed midsole material as claimed in claim 1, wherein the antioxidant is antioxidant 168: 3(2, 4-di-tert-butylphenyl) phosphite, antioxidant 1076: 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, antioxidant 1098: n, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexamethylenediamine), antioxidant 1010: one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
7. The TPEE foamed midsole material of claim 1, wherein said lubricant is one or more of wax powder, non-polar PE wax, talc, low-polymer stearate, and zinc stearate.
8. The foamed shoe midsole material of TPEE according to claim 1, wherein said cross-linking agent is one or more of dicumyl peroxide, t-butyl cumyl peroxide, dibenzoyl peroxide, di-t-butylperoxy diisopropylbenzene.
9. The TPEE foamed midsole material of claim 1, wherein said cell stabilizer is one or more of acrylic compounds.
10. A preparation process of a foaming shoe midsole material made of TPEE material is characterized by comprising the following steps:
(1) drying before feeding: putting the TPEE particles into a vacuum drying oven to be dried for 3 hours at the temperature of 80 ℃;
(2) storing materials, primary melting: after the raw materials are dried, the raw materials enter a machine barrel through a weightlessness type limited precise feeding machine, heating, shearing and plasticizing are carried out on the front section of a screw rod of a double-extruder, and after the raw materials enter a metering section and are uniformly plasticized, primary melting TPEE molten gel is formed;
(3) injecting supercritical foaming gas: pressurizing a supercritical fluid by a high-pressure pump, injecting the pressurized supercritical fluid into the thermoplastic polyester elastic melt in the cylinder at a constant flow rate through the control of a metering valve, mixing for the first time, and mixing the thermoplastic polyester/supercritical fluid two-phase system into a liquid homogeneous system through a mixing element at the head of a screw and a static mixer;
(4) secondary plasticization: the gas-saturated homogeneous phase liquid TPEE system enters a single screw to be plasticized for the second time, so that the gas-saturated homogeneous phase system becomes a supersaturated system and a large number of micropore gas nuclei are formed;
(5) injection molding: injecting the prepared TPEE foaming body by using a special-shaped intercepting type porous injection nozzle by adopting a special injection process, injecting the prepared TPEE foaming body into a female die below in a foaming strip mode, moving the female die back and forth at a speed until the female die is stacked and filled with foaming materials, and then closing the male die up and down for hot press molding;
(6) cooling and shaping: after the forming process is finished, the pressure in the cavity is reduced to enable the bubbles to expand, meanwhile, the cooling effect of the mold enables the bubbles to be solidified and shaped, and after the forming process is finished, the mold is opened and is demoulded to finish the foaming shoe insole made of TPEE material.
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