CN107698860B - High-resilience composition foaming material for soles and preparation method thereof - Google Patents
- ️Tue Sep 08 2020
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
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
-
- 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
- C08J9/06—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 chemical blowing agent
- C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- 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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
- A43B13/18—Resilient soles
- A43B13/187—Resiliency achieved by the features of the material, e.g. foam, non liquid materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- 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
- C08J9/06—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 chemical blowing agent
- C08J9/08—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 chemical blowing agent developing carbon dioxide
-
- 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
- C08J9/06—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 chemical blowing agent
- C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
-
- 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
- C08J9/06—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 chemical blowing agent
- C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
-
- 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
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- 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
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/06—Polyurethanes from polyesters
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
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
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:
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
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
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)
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
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:
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:
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:
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:
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:
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:
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:
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:
the preparation method of the TPU/EVA alloy comprises the following steps: a. 100 parts by weight of polyether type TPU elastomer
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.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711033480.1A CN107698860B (en) | 2017-10-30 | 2017-10-30 | High-resilience composition foaming material for soles and preparation method thereof |
PCT/CN2017/110801 WO2019085008A1 (en) | 2017-10-30 | 2017-11-14 | High resilience composition foaming material for soles and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711033480.1A CN107698860B (en) | 2017-10-30 | 2017-10-30 | High-resilience composition foaming material for soles and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107698860A CN107698860A (en) | 2018-02-16 |
CN107698860B true CN107698860B (en) | 2020-09-08 |
Family
ID=61176824
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711033480.1A Active CN107698860B (en) | 2017-10-30 | 2017-10-30 | High-resilience composition foaming material for soles and preparation method thereof |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN107698860B (en) |
WO (1) | WO2019085008A1 (en) |
Families Citing this family (16)
* Cited by examiner, † Cited by third partyPublication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108659516B (en) * | 2018-04-28 | 2021-03-12 | 广州顺力聚氨酯科技有限公司 | Mixing type polyurethane cross-linking foaming material and preparation method thereof |
US20200017658A1 (en) * | 2018-07-10 | 2020-01-16 | Nano And Advanced Materials Institute Limited | Germ-repellent elastomer |
CN110698750A (en) * | 2018-07-10 | 2020-01-17 | 安踏(中国)有限公司 | High-elasticity wear-resistant EVA composite foam material, preparation method thereof and composition for preparing material |
CN109233178B (en) * | 2018-07-24 | 2022-03-15 | 泉州泰亚鞋业有限公司 | Ultra-light shock-absorbing wear-resistant foamed shoe material and manufacturing method thereof |
CN109181227A (en) * | 2018-08-21 | 2019-01-11 | 扬州朗劲塑胶实业有限公司 | A kind of TPR footwear material transparent filler and preparation method thereof |
US11225569B2 (en) * | 2018-10-17 | 2022-01-18 | Braskem America, Inc. | Blends of thermoplastic urethanes and ethylene vinyl acetate copolymers |
CN109384904A (en) * | 2018-11-26 | 2019-02-26 | 福建省晋江泉发骑士鞋业有限公司 | A kind of ETPU sole material and its preparation method and application |
CN110551337A (en) * | 2019-10-14 | 2019-12-10 | 上海联景高分子材料有限公司 | EVA and TPU melt blending to prepare elastomer alloy and composition foaming material thereof |
WO2021072665A1 (en) * | 2019-10-16 | 2021-04-22 | 加久企业股份有限公司 | Tpu foam sole manufacturing process and product thereof |
CN110724375A (en) * | 2019-11-12 | 2020-01-24 | 福建安达福新材料科技有限公司 | TPU/EVA supercritical foaming composite material and preparation method thereof |
CN113045815A (en) * | 2019-12-27 | 2021-06-29 | 陈志勇 | Sole material composition, sole material and manufacturing method thereof |
CN113912874B (en) * | 2020-07-08 | 2024-05-10 | 驰绿国际股份有限公司 | Recycling PET plastic bottles to make PET composite material masterbatch and its preparation method and application in foamed shoe materials |
CN112662045A (en) * | 2020-12-22 | 2021-04-16 | 福建省莆田市联盛鞋业有限公司 | EVA composition for midsole of shoe sole, midsole of shoe sole and preparation method and application of EVA composition |
CN114672062B (en) * | 2022-03-25 | 2023-05-26 | 南京工程学院 | Modified foaming agent and microcellular foamed styrenic thermoplastic elastomer |
CN115305025A (en) * | 2022-08-01 | 2022-11-08 | 广东汇齐新材料有限公司 | Composite hot melt adhesive film for shoe sole and preparation method thereof |
CN115926101B (en) * | 2023-02-14 | 2023-06-09 | 旭川化学(苏州)有限公司 | Low-temperature-resistant resin for polyurethane sole, and preparation method and application thereof |
Citations (1)
* Cited by examiner, † Cited by third partyPublication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105860245A (en) * | 2016-06-02 | 2016-08-17 | 泉州市晋科技术检测有限公司 | Shoes for old people and preparation method thereof |
Family Cites Families (6)
* Cited by examiner, † Cited by third partyPublication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE602004018903D1 (en) * | 2003-02-14 | 2009-02-26 | Depuy Spine Inc | IN-SITU MANUFACTURED INTERVERTEBRALE FUSION DEVICE |
JP2008110176A (en) * | 2006-10-31 | 2008-05-15 | Ki Shoken | Shoe making method |
US20130225020A1 (en) * | 2012-02-24 | 2013-08-29 | Kraton Polymers Us Llc | High flow, hydrogenated styrene-butadiene-styrene block copolymer and applications |
CN106867231A (en) * | 2017-01-23 | 2017-06-20 | 美瑞新材料股份有限公司 | The technique that a kind of In Situ Compatibilization prepares TPU alloy materials |
CN107090118A (en) * | 2017-04-28 | 2017-08-25 | 黎明职业大学 | Double hardness foaming sole materials of a kind of EVA TPU and preparation method thereof |
CN107151373A (en) * | 2017-05-22 | 2017-09-12 | 美瑞新材料股份有限公司 | A kind of expanded material composition with high resilience and preparation method thereof |
-
2017
- 2017-10-30 CN CN201711033480.1A patent/CN107698860B/en active Active
- 2017-11-14 WO PCT/CN2017/110801 patent/WO2019085008A1/en active Application Filing
Patent Citations (1)
* Cited by examiner, † Cited by third partyPublication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105860245A (en) * | 2016-06-02 | 2016-08-17 | 泉州市晋科技术检测有限公司 | Shoes for old people and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
WO2019085008A1 (en) | 2019-05-09 |
CN107698860A (en) | 2018-02-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107698860B (en) | 2020-09-08 | High-resilience composition foaming material for soles and preparation method thereof |
KR102189552B1 (en) | 2020-12-14 | Manufacturing process of in-situ compatibilization of TPU alloy material |
CN108102338B (en) | 2021-02-05 | Foaming shoe insole |
WO2018214208A1 (en) | 2018-11-29 | Composition for foaming material with high rebound resilience and preparation method therefor |
CN109111720B (en) | 2021-02-26 | Ultra-light high-resilience ETPU composite damping shoe midsole material and forming method thereof |
CN110551337A (en) | 2019-12-10 | EVA and TPU melt blending to prepare elastomer alloy and composition foaming material thereof |
CN105801998B (en) | 2018-03-02 | A kind of thermoplastic polyurethane composite foam material and preparation method thereof |
CN108559057B (en) | 2021-02-12 | Novel composite foam material and preparation method thereof |
CN107828205B (en) | 2020-10-02 | Vulcanized and crosslinked foamed polyurethane rubber compound particle and preparation method and forming process thereof |
CN107090118A (en) | 2017-08-25 | Double hardness foaming sole materials of a kind of EVA TPU and preparation method thereof |
TW201829523A (en) | 2018-08-16 | Thermoplastic polyurethane resin for foaming and production method thereof, and molded article |
EP1786857B2 (en) | 2016-03-30 | Low density polyurethane integral skin foam system prepared using expandable microspheres and water as coblowing agent |
CN108774378B (en) | 2021-04-06 | High-elastic shock-absorption rubber plastic material, shock-absorption high-elastic sole and preparation process thereof |
JP7582936B2 (en) | 2024-11-13 | Thermoplastic elastomer-based foams |
CN104072716A (en) | 2014-10-01 | Polyurethane elastomer and sole made from same |
CN114573904B (en) | 2023-07-18 | Foaming material for light high-elasticity compression-resistant shoes |
CN111423837A (en) | 2020-07-17 | TPU hot melt adhesive and preparation method thereof |
CN113754857A (en) | 2021-12-07 | Polyurethane elastomer for quickly-formed low-temperature-resistant shoe material and preparation method thereof |
CN111995728B (en) | 2022-04-19 | Non-polar modified TPU (thermoplastic polyurethane) for shoe material and preparation method thereof |
CN111777788B (en) | 2023-04-18 | Double-component stock solution of high-elasticity low-density polyurethane shoe material and preparation method thereof |
CN112795062A (en) | 2021-05-14 | Wear-resistant rubber foamed sports shoe material and preparation method thereof |
CN112574379B (en) | 2022-07-12 | Foaming material based on carbamate copolymer and preparation method thereof |
KR20210005658A (en) | 2021-01-14 | Foam based on thermoplastic elastomer |
KR20210005657A (en) | 2021-01-14 | Foam based on thermoplastic elastomer |
CN116461035A (en) | 2023-07-21 | Preparation process of supercritical foaming material and supercritical foaming material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
2018-02-16 | PB01 | Publication | |
2018-02-16 | PB01 | Publication | |
2018-03-16 | SE01 | Entry into force of request for substantive examination | |
2018-03-16 | SE01 | Entry into force of request for substantive examination | |
2019-07-16 | CB03 | Change of inventor or designer information | |
2019-07-16 | CB03 | Change of inventor or designer information |
Inventor after: Song Hongwei Inventor after: Wang Guangfu Inventor after: Zhan Zhensheng Inventor after: Zhang Sheng Inventor after: Wang Renhong Inventor before: Wang Guangfu Inventor before: Zhan Zhensheng Inventor before: Song Hongwei Inventor before: Zhang Sheng Inventor before: Wang Renhong |
2020-09-08 | GR01 | Patent grant | |
2020-09-08 | GR01 | Patent grant |