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CN107698860B - High-resilience composition foaming material for soles and preparation method thereof - Google Patents

  • ️Tue Sep 08 2020
High-resilience composition foaming material for soles and preparation method thereof Download PDF

Info

Publication number
CN107698860B
CN107698860B CN201711033480.1A CN201711033480A CN107698860B CN 107698860 B CN107698860 B CN 107698860B CN 201711033480 A CN201711033480 A CN 201711033480A CN 107698860 B CN107698860 B CN 107698860B Authority
CN
China
Prior art keywords
mixing
eva
parts
foaming
weight
Prior art date
2017-10-30
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711033480.1A
Other languages
Chinese (zh)
Other versions
CN107698860A (en
Inventor
宋红玮
王光阜
战振生
张生
王仁鸿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Miracll Chemicals Co Ltd
Original Assignee
Miracll Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
2017-10-30
Filing date
2017-10-30
Publication date
2020-09-08
2017-10-30 Application filed by Miracll Chemicals Co Ltd filed Critical Miracll Chemicals Co Ltd
2017-10-30 Priority to CN201711033480.1A priority Critical patent/CN107698860B/en
2017-11-14 Priority to PCT/CN2017/110801 priority patent/WO2019085008A1/en
2018-02-16 Publication of CN107698860A publication Critical patent/CN107698860A/en
2020-09-08 Application granted granted Critical
2020-09-08 Publication of CN107698860B publication Critical patent/CN107698860B/en
Status Active legal-status Critical Current
2037-10-30 Anticipated expiration legal-status Critical

Links

  • 239000000463 material Substances 0.000 title claims abstract description 112
  • 238000005187 foaming Methods 0.000 title claims abstract description 102
  • 239000000203 mixture Substances 0.000 title claims abstract description 65
  • 238000002360 preparation method Methods 0.000 title claims abstract description 19
  • 239000000956 alloy Substances 0.000 claims abstract description 32
  • 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
  • 238000002156 mixing Methods 0.000 claims description 97
  • 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 30
  • 238000002347 injection Methods 0.000 claims description 20
  • 239000007924 injection Substances 0.000 claims description 20
  • 239000004156 Azodicarbonamide Substances 0.000 claims description 15
  • XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 15
  • 235000019399 azodicarbonamide Nutrition 0.000 claims description 15
  • 238000001816 cooling Methods 0.000 claims description 13
  • 238000001035 drying Methods 0.000 claims description 10
  • 239000003999 initiator Substances 0.000 claims description 10
  • 238000007493 shaping process Methods 0.000 claims description 10
  • 238000005303 weighing Methods 0.000 claims description 10
  • 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
  • 238000005520 cutting process Methods 0.000 claims description 8
  • 229920000570 polyether Polymers 0.000 claims description 8
  • FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
  • 239000000806 elastomer Substances 0.000 claims description 3
  • XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
  • 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 93
  • 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 92
  • 239000004433 Thermoplastic polyurethane Substances 0.000 abstract description 48
  • 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 47
  • 239000004088 foaming agent Substances 0.000 abstract description 6
  • 239000003431 cross linking reagent Substances 0.000 abstract description 5
  • 239000000945 filler Substances 0.000 abstract description 3
  • DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 81
  • 238000012360 testing method Methods 0.000 description 16
  • XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 13
  • 238000000034 method Methods 0.000 description 12
  • 238000007906 compression Methods 0.000 description 10
  • 230000006835 compression Effects 0.000 description 10
  • 229920005862 polyol Polymers 0.000 description 10
  • 150000003077 polyols Chemical class 0.000 description 10
  • 238000004519 manufacturing process Methods 0.000 description 9
  • UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 8
  • 239000005057 Hexamethylene diisocyanate Substances 0.000 description 8
  • 230000000704 physical effect Effects 0.000 description 8
  • 239000013543 active substance Substances 0.000 description 7
  • VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
  • 239000012752 auxiliary agent Substances 0.000 description 6
  • 150000001875 compounds Chemical class 0.000 description 6
  • 239000006260 foam Substances 0.000 description 6
  • 239000006261 foam material Substances 0.000 description 6
  • 238000005469 granulation Methods 0.000 description 5
  • 230000003179 granulation Effects 0.000 description 5
  • UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
  • GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
  • RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
  • OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
  • ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 3
  • HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
  • 229910052788 barium Inorganic materials 0.000 description 3
  • 229910000019 calcium carbonate Inorganic materials 0.000 description 3
  • 230000000052 comparative effect Effects 0.000 description 3
  • 239000012948 isocyanate Substances 0.000 description 3
  • 150000002513 isocyanates Chemical group 0.000 description 3
  • 229920005906 polyester polyol Polymers 0.000 description 3
  • 230000008569 process Effects 0.000 description 3
  • 238000012545 processing Methods 0.000 description 3
  • 239000002994 raw material Substances 0.000 description 3
  • 239000001509 sodium citrate Substances 0.000 description 3
  • NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
  • DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
  • SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
  • NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
  • 239000004970 Chain extender Substances 0.000 description 2
  • 229920000103 Expandable microsphere Polymers 0.000 description 2
  • ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
  • 239000005058 Isophorone diisocyanate Substances 0.000 description 2
  • VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
  • XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
  • CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
  • 239000004927 clay Substances 0.000 description 2
  • NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
  • 238000012986 modification Methods 0.000 description 2
  • 230000004048 modification Effects 0.000 description 2
  • JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
  • 229920000642 polymer Polymers 0.000 description 2
  • 238000003825 pressing Methods 0.000 description 2
  • 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
  • 235000017557 sodium bicarbonate Nutrition 0.000 description 2
  • 239000004408 titanium dioxide Substances 0.000 description 2
  • FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
  • 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
  • ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
  • 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
  • LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
  • VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
  • 239000005977 Ethylene Substances 0.000 description 1
  • 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
  • 239000002202 Polyethylene glycol Substances 0.000 description 1
  • UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
  • QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
  • KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
  • 125000004018 acid anhydride group Chemical group 0.000 description 1
  • 150000001413 amino acids Chemical class 0.000 description 1
  • 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
  • 239000001099 ammonium carbonate Substances 0.000 description 1
  • 239000003963 antioxidant agent Substances 0.000 description 1
  • 230000003078 antioxidant effect Effects 0.000 description 1
  • -1 argil Chemical compound 0.000 description 1
  • 230000009286 beneficial effect Effects 0.000 description 1
  • 125000004432 carbon atom Chemical group C* 0.000 description 1
  • 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
  • 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
  • 230000007547 defect Effects 0.000 description 1
  • 238000011161 development Methods 0.000 description 1
  • 150000004985 diamines Chemical class 0.000 description 1
  • 150000002009 diols Chemical class 0.000 description 1
  • FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
  • 229920001971 elastomer Polymers 0.000 description 1
  • 125000003700 epoxy group Chemical group 0.000 description 1
  • 239000003822 epoxy resin Substances 0.000 description 1
  • VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
  • 229920006258 high performance thermoplastic Polymers 0.000 description 1
  • 239000003562 lightweight material Substances 0.000 description 1
  • 239000000314 lubricant Substances 0.000 description 1
  • ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
  • 239000004005 microsphere Substances 0.000 description 1
  • 238000000465 moulding Methods 0.000 description 1
  • 229920001610 polycaprolactone Polymers 0.000 description 1
  • 239000004632 polycaprolactone Substances 0.000 description 1
  • 239000004417 polycarbonate Substances 0.000 description 1
  • 229920000515 polycarbonate Polymers 0.000 description 1
  • 229920000647 polyepoxide Polymers 0.000 description 1
  • 229920001223 polyethylene glycol Polymers 0.000 description 1
  • 229920003225 polyurethane elastomer Polymers 0.000 description 1
  • 238000011160 research Methods 0.000 description 1
  • 238000012827 research and development Methods 0.000 description 1
  • 235000011083 sodium citrates Nutrition 0.000 description 1
  • 239000000126 substance Substances 0.000 description 1
  • 230000009466 transformation Effects 0.000 description 1
  • 239000011787 zinc oxide Substances 0.000 description 1
  • XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-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 chemical blowing agent
    • C08J9/10Working-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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102Azo-compounds
    • C08J9/103Azodicarbonamide
    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00Soles; Sole-and-heel integral units
    • A43B13/02Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04Plastics, rubber or vulcanised fibre
    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00Soles; Sole-and-heel integral units
    • A43B13/14Soles; Sole-and-heel integral units characterised by the constructive form
    • A43B13/18Resilient soles
    • A43B13/187Resiliency achieved by the features of the material, e.g. foam, non liquid materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014Use of organic additives
    • C08J9/0023Use of organic additives containing oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-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 chemical blowing agent
    • C08J9/08Working-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 chemical blowing agent developing carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-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 chemical blowing agent
    • C08J9/10Working-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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102Azo-compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-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 chemical blowing agent
    • C08J9/10Working-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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/02CO2-releasing, e.g. NaHCO3 and citric acid
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/04N2 releasing, ex azodicarbonamide or nitroso compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04Polyurethanes
    • C08J2475/06Polyurethanes from polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract

The invention relates to a high-resilience composition foaming material for soles and a preparation method thereof, wherein the high-resilience composition foaming material comprises the following components in parts by weight: 100 parts of ethylene-vinyl acetate copolymer EVA; 1-70 parts of thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy; 0.1-10 parts of foaming agent; 0.01-10 parts of a crosslinking agent; 0-20 parts of a filler; the high-resilience composition foaming material for the soles, disclosed by the invention, utilizes the TPU/EVA alloy to play a role of a compatibilizer, so that an EVA/TPU interpenetrating network structure (IPN) is formed, and a TPU component is introduced into a conventional EVA foaming system, so that the problem that the performance of the final composition foaming material is reduced due to poor compatibility of the two is solved.

Description

High-resilience composition foaming material for soles and preparation method thereof

Technical Field

The invention relates to a foaming material and a preparation method thereof, in particular to a high-resilience composition foaming material for soles and a preparation method thereof, and belongs to the technical field of lightweight materials.

Background

Ethylene-vinyl acetate copolymers are prepared by copolymerizing ethylene (E) and Vinyl Acetate (VA), known by the English name of ethylene vinyl acetate, EVA for short. The foamed EVA has the advantages of light weight, softness and comfortable wearing as the main material of the existing sole material, especially the sole material of sports shoes, but after the EVA sole foamed material with high foaming rate is worn for a long time, the resilience loss of the foamed EVA material is very large, the permanent deformation is large, the mechanical property is seriously reduced, the wear resistance is poor and the like, and the application of the foamed EVA sole foamed material in the field of shoe materials is seriously influenced. Therefore, developing an EVA foam material for shoe soles, which has excellent resilience and a high expansion ratio, is a goal pursued by many colleges and enterprises.

Disclosure of Invention

The invention provides a high-resilience composition foaming material for soles and a preparation method thereof, aiming at the defects of an EVA sole material with high foaming ratio.

The technical scheme for solving the technical problems is as follows:

the high-resilience composition foaming material for the shoe sole is characterized by comprising the following components in parts by weight:

Figure BDA0001449849070000011

Figure BDA0001449849070000021

wherein, the thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy can be prepared by any one of the following methods:

the first method, see patent No. 201710058676X, comprises the steps of 1) premixing 100 weight parts of TPU raw material, adding into the feed inlet of a double screw extruder, injecting 5-95 weight parts of ethylene-vinyl acetate copolymer and 0.1-10 weight parts of double active substance into the double screw extruder through side feeding, wherein the two are not in sequence, and 0.1-5 weight parts of auxiliary agent is added into the TPU raw material or the mixture of the ethylene-vinyl acetate copolymer and the double active substance;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 50-250 ℃ and granulating;

3) drying the granulated product obtained in the step 2) to obtain the granulated product;

the second method comprises the following steps: uniformly mixing 100 parts by weight of TPU, 5-95 parts by weight of EVA, 0.1-10 parts by weight of double-active substance and 0.1-5 parts by weight of auxiliary agent, processing the mixture by an extruder, and granulating to obtain the compound;

the third method comprises the following steps: uniformly mixing 100 parts by weight of TPU, 5-95 parts by weight of EVA, 0.1-10 parts by weight of double-active substance and 0.1-5 parts by weight of auxiliary agent, processing the mixture by an open mill, and granulating to obtain the high-performance thermoplastic polyurethane elastomer;

the method IV comprises the following steps: uniformly mixing 100 parts by weight of TPU, 5-95 parts by weight of EVA, 0.1-10 parts by weight of double-active substance and 0.1-5 parts by weight of auxiliary agent, processing the mixture by an internal mixer, and granulating to obtain the thermoplastic polyurethane elastomer;

the double active substance is a compound containing acid anhydride group, carboxyl-COOH, hydroxyl-OH, amino-NH or-NH2A compound of one or more of an isocyanate group-NCO, an epoxy group, and the auxiliary agent comprises an initiator.

EVA materials of the present invention are well known and are conventional for use in the foamed shoe material art, such as those available from DuPont

Figure BDA0001449849070000022

Further, the double-active substance is one of maleic anhydride, glycidyl methacrylate, acrylic acid, methyl methacrylate, butyl acrylate, acrylamide, allyl polyethylene glycol, amino acid and epoxy resin.

Further, the TPU raw material in the first method comprises polymer polyol, chain extender and isocyanate, the polymer polyol is one or a compound of more of polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol and hydroxyl-terminated polybutadiene diol, the chain extender is micromolecular dihydric alcohol or diamine containing less than 12 carbon atoms, the isocyanate is one or a compound of toluene diisocyanate TDI, diphenylmethane diisocyanate MDI, hexamethylene diisocyanate HDI, dicyclohexylmethane diisocyanate H12MDI, isophorone diisocyanate IPDI and xylylene diisocyanate XDI, the hardness of the TPU in the second method, the third method and the fourth method is 40-95Shore A, preferably 60-90Shore A, particularly preferably 70-85Shore A, as measured according to ASTM D2240; melt flow rate of 5-100g/10min, measured according to ASTM-1238 at 200 ℃ with 5Kg weight applied.

Further, the ethylene-vinyl acetate copolymer in the thermoplastic polyurethane/ethylene-vinyl acetate alloy has a vinyl acetate content of 10 to 80 wt%, preferably a vinyl acetate content of 20 to 50 wt%, and most preferably a vinyl acetate content of 25 to 45 wt%.

Further, the foaming agent is one or a mixture of several of exothermic foaming agent, endothermic foaming agent and foaming microsphere, preferably, the foaming agent is one or a mixture of several of azodicarbonamide, azodiisobutyronitrile, barium azodicarboxylate, 4, 4' -oxybis-benzenesulfonylhydrazide, p-toluene sulfonyl hydrazide, sodium bicarbonate, sodium citrate, ammonium bicarbonate and expandable microsphere, wherein the expandable microsphere is well known and available from AKZO Nobel Industries expand

Figure BDA0001449849070000031

And (4) series.

Further, the crosslinking agent is one or a mixture of more of dicumyl peroxide, di-tert-butylperoxyisopropyl benzene, azobisisobutyronitrile, azoisobutyronitrile formamide, azodicyclohexyl cyanogen and dimethyl azodiisobutyrate.

Further, the filler is one or a mixture of more of talcum powder, calcium carbonate, argil, sulfate and toner.

Furthermore, the composition foaming material also comprises an antioxidant, a lubricant, a UV resistant auxiliary agent, an auxiliary crosslinking agent and a foaming promoter, wherein the auxiliary crosslinking agent is a compound containing 2 or more carbon-carbon double bonds, and the foaming promoter is any one of zinc oxide and zinc stearate.

The invention also claims a preparation method of the high-resilience composition foaming material, which comprises the following steps:

1) weighing 100 parts by weight of EVA, 1-70 parts by weight of thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy, 0.1-10 parts by weight of foaming agent, 0.01-10 parts by weight of cross-linking agent and 0-20 parts by weight of filler, and putting into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture obtained in the step 1) into an internal mixer for mixing uniformly, controlling the mixing time to be 5-25 minutes, and the mixing temperature to be 100-150 ℃ to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, controlling the mixing time to be 5-30 minutes and the mixing temperature to be 80-200 ℃ to obtain a second-stage mixed material; 4) foaming and shaping: placing the second-stage mixed material obtained in the step 3) into a sole product mold, then placing the mold into a flat vulcanizing machine for mold pressing foaming, wherein the foaming temperature is 100-200 ℃, the foaming time is 1-10 minutes, and then cooling the mold to 10-50 ℃ to obtain the high-resilience EVA composition foamed sole material; or putting the second-stage mixed material obtained in the step 3) into a foaming shoe material device for primary injection foaming, wherein the injection temperature is controlled at 120-180 ℃, and the high-resilience EVA composition foaming sole material is obtained.

Further, the foamed shoe material device with one-time injection in the step 4) is an injection foaming molding machine.

Compared with the prior art, the high-resilience composition foaming material and the preparation method thereof provided by the invention have the following beneficial effects:

1) according to the high-resilience composition foaming material for the soles, the TPU/EVA alloy is used as a compatibilizer, an EVA/TPU interpenetrating network structure (IPN) is formed, and a TPU component is introduced into a conventional EVA foaming system, so that the problem that the performance of the final composition foaming material is reduced due to poor compatibility of the two components is solved;

2) by utilizing the excellent rebound resilience, wear resistance and mechanical property of the TPU, the rebound resilience, compression set and other properties of the foamed EVA sole material are greatly improved;

3) the process flow is simple, and the EVA foaming shoe material can be directly used in the existing mould pressing EVA foaming shoe material equipment or one-time injection EVA foaming shoe material equipment without equipment transformation or research, development and investment of new process equipment.

Detailed Description

The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.

Preparation of TPU/EVA alloy material

Example 1:

a process for preparing a TPU alloy material comprises the following steps:

1) 68 parts of polyester polyol with the molecular weight of 2000g/mol, 6 parts of BDO and 26 parts of diphenylmethane diisocyanate MDI (diphenylmethane diisocyanate), and injecting 95 parts of EVA, 10 parts of MAH (maleic anhydride) and 5 parts of initiator DCP (dicumyl peroxide) into a double-screw extruder through side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-200 ℃, controlling the temperature of a cooling zone to be 90-110 ℃, and carrying out underwater cutting granulation on the extruded material;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 2:

a process for preparing a TPU alloy material comprises the following steps:

1) 55 parts of polyester polyol with the molecular weight of 1500g/mol, 7 parts of BDO and 38 parts of diphenylmethane diisocyanate MDI (diphenylmethane diisocyanate) are added into a feed port of a double-screw extruder, and 75 parts of EVA (ethylene vinyl acetate), 5 parts of MAH (maleic anhydride) and 0.2 part of initiator DCP (dicumyl peroxide) are injected into the double-screw extruder through side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 50-250 ℃ and the temperature of a cooling zone to be 90-110 ℃, and cutting and granulating the extruded material under water;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 3:

a process for preparing a TPU alloy material comprises the following steps:

1) 70 parts by weight of a polyether polyol having a molecular weight of 1800g/mol, 5 parts of BDO and 25 parts of toluene diisocyanate TDI were added to the feed inlet of a twin-screw extruder, and 65 parts of EVA (Tri-well chemical)

Figure BDA0001449849070000061

150Y), 0.1 part of acrylic acid and 0.1 part of initiator DCP (dicumyl peroxide) are injected into a twin-screw extruder by side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 4:

a process for preparing a TPU alloy material comprises the following steps:

1) adding 45 parts by weight of polyether polyol with the molecular weight of 1000g/mol, 8 parts of BDO and 47 parts of toluene diisocyanate TDI into a feed port of a double-screw extruder, and injecting 34 parts of EVA, 0.5 part of acrylamide and 0.15 part of initiator DCP (dicumyl peroxide) into the double-screw extruder through side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-170 ℃, controlling the temperature of a cooling zone to be 90-110 ℃, and carrying out underwater cutting granulation on the extruded material;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 5:

a process for preparing a TPU alloy material comprises the following steps:

1) adding 45 parts by weight of polyether polyol with the molecular weight of 1800g/mol, 8 parts of BDO and 47 parts of hexamethylene diisocyanate HDI into a feed port of a double-screw extruder, and injecting 45 parts of EVA, 1.5 parts of acrylamide and 0.25 part of initiator DCP (dicumyl peroxide) into the double-screw extruder through side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-170 ℃, controlling the temperature of a cooling zone to be 90-110 ℃, and carrying out underwater cutting granulation on the extruded material;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 6:

a process for preparing a TPU alloy material comprises the following steps:

1) adding 45 parts by weight of polyether polyol with the molecular weight of 1800g/mol, 8 parts of BDO and 47 parts of hexamethylene diisocyanate HDI into a feed port of a double-screw extruder, and injecting 5 parts of EVA, 0.1 part of methyl methacrylate and 1 part of initiator DCP (dicumyl peroxide) into the double-screw extruder through side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-170 ℃, controlling the temperature of a cooling zone to be 90-110 ℃, and carrying out underwater cutting granulation on the extruded material;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 7:

a process for preparing a TPU alloy material comprises the following steps:

1) adding 45 parts by weight of polyether polyol with the molecular weight of 1800g/mol, 8 parts of BDO and 47 parts of hexamethylene diisocyanate HDI into a feed inlet of a double-screw extruder, and injecting 75 parts of EVA, 6 parts of butyl acrylate and 2 parts of initiator DCP (dicumyl peroxide) into the double-screw extruder through side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-170 ℃, controlling the temperature of a cooling zone to be 90-110 ℃, and carrying out underwater cutting granulation on the extruded material;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 8:

a process for preparing a TPU alloy material comprises the following steps:

1) 100 parts by weight of polyether type TPU elastomer

Figure BDA0001449849070000082

M70, 90 parts of EVA with 40 percent of VA, 1.5 parts of maleic anhydride and 0.25 part of initiator DCP (dicumyl peroxide) are placed in a high-speed mixer for premixing;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-170 ℃ and the temperature of a cooling zone to be 90-110 ℃, extruding the mixture obtained in the step 1) by the extruder, and cutting and granulating the extruded material under water; 3) drying the granulated product obtained in the step 2) to obtain the product.

The TPU/EVA alloy materials obtained in the examples 7 and 8 are applied to a high-resilience composition, and the specific composition, the preparation method and the properties of the composition are as follows:

high-resilience composition foaming material for soles

Example 9:

a high-resilience composition foaming material for soles comprises the following components in parts by weight:

Figure BDA0001449849070000081

the preparation process of the foaming material is as follows:

1) weighing EVA, TPU/EVA alloy, Azodicarbonamide (AC) and di-tert-butylperoxyisopropyl benzene (DCP) with corresponding weight, and putting the weighed materials into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer for mixing uniformly, setting the mixing temperature to be 100 ℃, and mixing for 10 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 100 ℃, and mixing is carried out for 5 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) placing the second mixed material obtained in the step 3) in a sole product mold, then placing the sole product mold in a flat vulcanizing machine for mold foaming, wherein the foaming time is 1 minute, the foaming temperature is 100 ℃, and then cooling the mold to 10 ℃ to obtain the high-resilience EVA composition sole foaming material.

The data of the physical property test results of the composition sole foaming material prepared by the steps and the existing EVA foaming products on the market are shown in Table 1.

TABLE 1

Item Test standard Unit of Example 9 product Market EVA foaming product
Density of ASTM-D792 g/cm3 0.2 0.25
Hardness of GB/T10807-2006 Shore 45 45
Tensile strength ISO1798-2008 MPa 5.0 1.5
Elongation at break ISO1798-2008 500 300
Tear strength GB/T10808-2006 N/mm 8 4.2
Rebound resilience GB/T6670-2008 60 50
Compression set GB/T6669-2008 25 35
Wear resistance DIN53516 Mm3 400 500

Example 10:

a high-resilience composition foaming material for soles comprises the following components in parts by weight:

Figure BDA0001449849070000091

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, azodicarbonamide and dicumyl peroxide (DCP) with corresponding weight and VA content of 20% and putting the EVA, the TPU/EVA alloy, the azodicarbonamide and the DCP into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer for mixing uniformly, setting the mixing temperature at 150 ℃, and mixing for 15 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 120 ℃, and mixing is carried out for 10 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) putting the second mixed material obtained in the step 3) into an injection foaming forming machine for primary injection foaming, wherein the injection temperature is controlled at 150 ℃, and the high-resilience EVA composition foamed sole material is obtained.

The data of the physical property test results of the composition foam material prepared by the above steps and the existing EVA foam products on the market are shown in Table 2.

TABLE 2

Item Test standard Unit of EXAMPLE 10 product Market EVA foaming product
Density of ASTM-D792 g/cm3 0.21 0.25
Hardness of GB/T10807-2006 Shore 45 45
Tensile strength ISO1798-2008 MPa 6 1.5
Elongation at break ISO1798-2008 550 300
Tear strength GB/T10808-2006 N/mm 10.4 4.2
Rebound resilience of ball drop GB/T6670-2008 58 50
Compression set GB/T6669-2008 20 35
Wear resistance DIN53516 Mm3 380 500

Example 11:

a high-resilience composition foaming material for soles comprises the following components in parts by weight:

Figure BDA0001449849070000101

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, sodium bicarbonate and dicumyl peroxide (DCP) with corresponding weight and the VA content of 20 percent, and putting the EVA, the TPU/EVA alloy, the sodium bicarbonate and the DCP into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer, setting the mixing temperature at 120 ℃, and mixing for 25 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 110 ℃, and mixing is carried out for 30 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) placing the second mixed material obtained in the step 3) into a sole product mold, then placing the sole product mold into a flat vulcanizing machine for mold foaming, wherein the foaming time is 10 minutes, the foaming temperature is 130 ℃, and then cooling the mold to 30 ℃ to obtain the high-resilience EVA composition sole foaming material.

The data of the physical property test results of the composition sole foaming material prepared by the steps and the existing EVA foaming products on the market are shown in Table 3.

TABLE 3

Item Test standard Unit of EXAMPLE 11 product Market EVA foaming product
Density of ASTM-D792 g/cm3 0.22 0.25
Hardness of GB/T10807-2006 Shore 45 45
Tensile strength ISO1798-2008 MPa 5.5 1.5
Elongation at break ISO1798-2008 510 300
Tear strength GB/T10808-2006 N/mm 8.8 4.2
Rebound resilience of ball drop GB/T6670-2008 61 50
Compression set GB/T6669-2008 22 35
Wear resistance DIN53516 Mm3 350 500

Example 12:

a high-resilience composition foaming material for soles comprises the following components in parts by weight:

Figure BDA0001449849070000111

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, Azodicarbonamide (AC) and dicumyl peroxide (DCP) with corresponding weight and 25 percent of VA content, and putting the EVA, the TPU/EVA alloy, the Azodicarbonamide (AC) and the DCP into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer, setting the mixing temperature at 140 ℃, and mixing for 10 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 120 ℃, and mixing is carried out for 15 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) putting the second mixed material obtained in the step 3) into a rotary disc type injection foaming machine for primary injection foaming, wherein the injection temperature is controlled at 150 ℃, and finally the high-resilience EVA composition sole foaming material is obtained.

The data of the physical property test results of the composition foam material prepared by the above steps and the existing EVA foam products on the market are shown in Table 4.

TABLE 4

Item Test standard Unit of EXAMPLE 12 product Market EVA foaming product
Density of ASTM-D792 g/cm3 0.22 0.25
Hardness of GB/T10807-2006 Shore 45 45
Tensile strength ISO1798-2008 MPa 9.2 1.5
Elongation at break ISO1798-2008 480 300
Tear strength GB/T10808-2006 N/mm 10.4 4.2
Rebound resilience of ball drop GB/T6670-2008 62 50
Compression set GB/T6669-2008 18 35
Wear resistance DIN53516 Mm3 400 500

Example 13:

a high-resilience composition foaming material for soles comprises the following components in parts by weight:

Figure BDA0001449849070000121

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, p-toluenesulfonyl hydrazide, di-tert-butylperoxyisopropyl benzene and calcium carbonate with corresponding weight and 25 percent of VA content, and putting the EVA, the TPU/EVA alloy, the p-toluenesulfonyl hydrazide, the di-tert-butylperoxyisopropyl benzene and the calcium carbonate into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer, setting the mixing temperature at 100 ℃, and mixing for 10 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 120 ℃, and mixing is carried out for 20 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) putting the second mixed material obtained in the step 3) into a rotary disc type injection foaming machine for primary injection foaming, wherein the injection temperature is controlled at 120 ℃, and finally the high-resilience EVA composition sole foaming material is obtained.

The data of the physical property test results of the composition foam material prepared through the above steps and the existing EVA foam products on the market are shown in Table 5.

TABLE 5

Item Test standard Unit of EXAMPLE 13 product Market EVA foaming product
Density of ASTM-D792 g/cm3 0.23 0.25
Hardness of GB/T10807-2006 Shore 45 45
Tensile strength ISO1798-2008 MPa 3.8 1.5
Elongation at break ISO1798-2008 500 300
Tear strength GB/T10808-2006 N/mm 6.0 4.2
Rebound resilience of ball drop GB/T6670-2008 62 50
Compression set GB/T6669-2008 20 35
Wear resistance DIN53516 Mm3 410 500

Example 14:

a high-resilience EVA composition foaming material for soles comprises the following components in parts by weight:

Figure BDA0001449849070000131

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, sodium citrate, di-tert-butylperoxyisopropyl benzene and titanium dioxide with corresponding weight and VA content of 25 percent, and putting the EVA, the TPU/EVA alloy, the sodium citrate, the di-tert-butylperoxyisopropyl benzene and the titanium dioxide into a high-speed mixer for primary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer, setting the mixing temperature at 100 ℃, and mixing for 10 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 120 ℃, and mixing is carried out for 15 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) placing the second mixed material obtained in the step 3) in a sole product mold, then placing the sole product mold in a flat vulcanizing machine for mold foaming, wherein the foaming time is 1 minute, the foaming temperature is 200 ℃, and then cooling the mold to 30 ℃ to obtain the high-resilience EVA composition sole foaming material.

The data of the physical property test results of the composition foam material prepared through the above steps and the existing EVA foam products on the market are shown in Table 6.

TABLE 6

Item Test standard Unit of EXAMPLE 14 product Market EVA foaming product
Density of ASTM-D792 g/cm3 0.24 0.25
Hardness of GB/T10807-2006 Shore 45 45
Tensile strength ISO1798-2008 MPa 3.0 1.5
Elongation at break ISO1798-2008 450 300
Tear strength GB/T10808-2006 N/mm 6.0 4.2
Rebound resilience of ball drop GB/T6670-2008 62 50
Compression set GB/T6669-2008 18 35
Wear resistance DIN53516 Mm3 380 500

Example 15:

a high-resilience composition foaming material for soles comprises the following components in parts by weight:

Figure BDA0001449849070000141

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, barium azodicarboxylate, di-tert-butylperoxyisopropyl benzene and pottery clay with corresponding weight and 25 percent of VA content, and putting the EVA, TPU/EVA alloy, barium azodicarboxylate, di-tert-butylperoxyisopropyl benzene and pottery clay into a high-speed mixer for primary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer, setting the mixing temperature at 100 ℃, and mixing for 10 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 120 ℃, and mixing is carried out for 25 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) putting the second mixed material obtained in the step 3) into a rotary disc type injection foaming machine for primary injection foaming, wherein the injection temperature is controlled at 180 ℃, and finally the high-resilience EVA composition sole foaming material is obtained.

The data of the physical property test results of the composition foam material prepared through the above steps and the existing EVA foam products on the market are shown in Table 7.

TABLE 7

Item Test standard Unit of EXAMPLE 15 product Market EVA foaming product
Density of ASTM-D792 g/cm3 0.18 0.25
Hardness of GB/T10807-2006 Shore 45 45
Tensile strength ISO1798-2008 MPa 2.8 1.5
Elongation at break ISO1798-2008 420 300
Tear strength GB/T10808-2006 N/mm 5.5 4.2
Rebound resilience of ball drop GB/T6670-2008 62 50
Compression set GB/T6669-2008 20 35
Wear resistance DIN53516 Mm3 380 500

Comparative example 1:

1) weighing 100 parts by weight of EVA with the VA content of 10%, 1 part by weight of TPU and 1 part by weight of azodicarbonamide AC, and putting the EVA, the TPU and the azodicarbonamide AC into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer, setting the mixing temperature to be 100 ℃, and mixing for 5 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 100 ℃, and mixing is carried out for 5 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) placing the second mixed material obtained in the step 3) in a sole product mold, placing the product mold in a flat vulcanizing machine for mold foaming, wherein the foaming time is 1 minute, the foaming temperature is 100 ℃, and then cooling the mold to 10 ℃ to obtain the EVA composition sole foaming material.

The physical property test data of the composition foam obtained in comparative example 1 and the product obtained in example 9 were compared, and the results are shown in Table 8:

TABLE 8

Item Test standard Unit of Example 9 Comparative example 1
Density of ASTM-D792 g/cm3 0.2 0.24
Hardness of GB/T10807-2006 Shore 45 45
Tensile strength ISO1798-2008 MPa 5.0 0.8
Elongation at break ISO1798-2008 500 220
Tear strength GB/T10808-2006 N/mm 8 3.5
Rebound resilience of ball drop GB/T6670-2008 60 52
Compression set GB/T6669-2008 25 48
Wear resistance DIN53516 Mm3 400 550

As can be seen from the data in tables 1 to 8, the product performance prepared by the technical scheme of the invention is obviously superior to the product performance prepared by directly mixing and foaming EVA and TPU or the conventional EVA foaming system; on the other hand, the invention greatly improves the performances of rebound resilience, compression set and the like of the existing foaming EVA material by utilizing the excellent wear resistance and mechanical property of the TPU, simplifies the process flow, does not need equipment modification or equipment research and development and investment, and reduces the production cost.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (1)

1. The high-resilience composition foaming material for the shoe sole is characterized by comprising the following components in parts by weight:

Figure FDA0002550910970000011

the preparation method of the TPU/EVA alloy comprises the following steps: a. 100 parts by weight of polyether type TPU elastomer

Figure FDA0002550910970000012

M70, 90 parts by weight of EVA with 40% of VA, 1.5 parts by weight of maleic anhydride and 0.25 part by weight of initiator dicumyl peroxide are placed in a high-speed mixer for premixing; b. controlling the temperature of a reaction zone of the double-screw extruder to be 140-170 ℃ and the temperature of a cooling zone to be 90-110 ℃, extruding the mixture obtained in the step a by the extruder, and cutting and granulating the extruded material under water; c. drying the granulated product obtained in the step b to obtain the product;

the preparation method of the high-resilience composition foaming material for the shoe sole comprises the following steps:

1) weighing EVA, TPU/EVA alloy, azodicarbonamide and dicumyl peroxide with corresponding weight and the VA content of 20 percent, and putting the EVA, the TPU/EVA alloy, the azodicarbonamide and the dicumyl peroxide into a high-speed mixer for primary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer for mixing uniformly, setting the mixing temperature at 150 ℃, and mixing for 15 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 120 ℃, and mixing is carried out for 10 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) putting the second mixed material obtained in the step 3) into an injection foaming forming machine for primary injection foaming, wherein the injection temperature is controlled at 150 ℃, and the material is obtained.

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