CN117534895A - Air pressure supported EVA (ethylene-vinyl acetate) chemical foaming sole material and preparation method thereof - Google Patents
Air pressure supported EVA (ethylene-vinyl acetate) chemical foaming sole material and preparation method thereof Download PDFInfo
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- CN117534895A CN117534895A CN202311460908.6A CN202311460908A CN117534895A CN 117534895 A CN117534895 A CN 117534895A CN 202311460908 A CN202311460908 A CN 202311460908A CN 117534895 A CN117534895 A CN 117534895A
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- air pressure
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- 239000000463 material Substances 0.000 title claims abstract description 144
- 238000005187 foaming Methods 0.000 title claims abstract description 138
- 239000000126 substance Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 15
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 title description 110
- 239000005038 ethylene vinyl acetate Substances 0.000 title description 110
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title description 110
- 239000004088 foaming agent Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 19
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 229920001971 elastomer Polymers 0.000 claims description 73
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- 239000003431 cross linking reagent Substances 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 39
- 238000007731 hot pressing Methods 0.000 claims description 38
- 239000002131 composite material Substances 0.000 claims description 37
- 238000001816 cooling Methods 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 31
- 238000000465 moulding Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000945 filler Substances 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 230000004888 barrier function Effects 0.000 claims description 21
- 239000006260 foam Substances 0.000 claims description 20
- 229920002943 EPDM rubber Polymers 0.000 claims description 18
- 239000004156 Azodicarbonamide Substances 0.000 claims description 17
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 17
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- 230000005540 biological transmission Effects 0.000 claims description 13
- 235000021355 Stearic acid Nutrition 0.000 claims description 11
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 11
- 229920006247 high-performance elastomer Polymers 0.000 claims description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000008117 stearic acid Substances 0.000 claims description 11
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920002614 Polyether block amide Polymers 0.000 claims description 9
- 238000000748 compression moulding Methods 0.000 claims description 9
- 229920005549 butyl rubber Polymers 0.000 claims description 8
- 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 claims description 8
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000004677 Nylon Substances 0.000 claims description 5
- 229920001778 nylon Polymers 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229920005555 halobutyl Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 230000001965 increasing effect Effects 0.000 abstract description 20
- 238000007906 compression Methods 0.000 abstract description 12
- 230000006835 compression Effects 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000000704 physical effect Effects 0.000 abstract description 5
- 230000003068 static effect Effects 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- ZPMCCZKDFLIVHD-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;1,2-di(propan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C.CC(C)C1=CC=CC=C1C(C)C ZPMCCZKDFLIVHD-UHFFFAOYSA-N 0.000 description 7
- 229920005557 bromobutyl Polymers 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 210000000497 foam cell Anatomy 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000007723 die pressing method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 210000001161 mammalian embryo Anatomy 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- CXUGZITZWVNSNK-UHFFFAOYSA-N 1-tert-butylperoxy-4-(2-tert-butylperoxypropan-2-yl)benzene Chemical compound C(C)(C)(C)OOC(C)(C)C1=CC=C(C=C1)OOC(C)(C)C CXUGZITZWVNSNK-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 229920006347 Elastollan Polymers 0.000 description 1
- 229920011453 Hytrel® 4056 Polymers 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920006099 Vestamid® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 230000006911 nucleation Effects 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- -1 peroxide free radical Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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
-
- 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
- C08J9/107—Nitroso 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
- 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
- C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08J2423/22—Copolymers of isobutene; butyl rubber
-
- 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
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention discloses an EVA chemical foaming sole material supported by air pressure and a preparation method thereof, which are characterized in that the melt strength is improved by temperature regulation and control through the improvement of an EVA chemical foaming secondary mould pressing process, and meanwhile, the matrix strength is matched with the air pressure when the foaming agent is balanced by greatly increasing the consumption of the foaming agent, so that the air pressure is improved, the air in the sole is enhanced, the prepared foaming material has ultra-light (density of 0.10+/-0.02) and ultra-elastic (rebound rate of 78%), and meanwhile, the compression modulus is higher under low hardness, and the foaming material is soft but not collapsed, so that the static soft comfort and the dynamic supporting stability of the foaming material are ensured. The physical properties of the sole can be compared with those of supercritical physical foaming materials, and the foaming process is greatly simplified compared with supercritical physical foaming.
Description
Technical Field
The invention belongs to the technical field of composite foaming sole materials, and particularly relates to an EVA (ethylene-vinyl acetate) chemical foaming sole material supported by air pressure and a preparation method thereof.
Background
The inflatable material is a material formed by sealing gas in the material, and can realize a spring effect through compression-release of high-pressure gas, and the effect is widely applied in aspects of shock absorption, rebound support and the like (such as tires, air springs, air cushion shoes, basketball and the like). EVA foaming materials are closed-cell and microporous foaming materials, and are also air-filled materials for sealing gas in the materials, and the functions of the EVA foaming materials can be realized through compression-release of the gas.
The traditional EVA foaming process mainly utilizes a chemical foaming agent (azodicarbonamide) to decompose at high temperature to generate gas, meanwhile, the peroxide is decomposed to generate free radicals to crosslink an EVA matrix material, the EVA matrix is expanded to complete foaming during mold opening, the crosslinking effect enables the pore walls to have enough strength to lock the gas, the pores are kept stable during mold opening pore growth, and meanwhile, the crosslinked EVA foaming material has certain strength, so that the EVA foaming material can be used in a certain temperature range. From the influence of temperature on the cells, the foaming temperature is 170-180 ℃, namely the die opening expansion temperature is 170-180 ℃, the pressure of gas is high at the moment according to PV=nRT, the strength of a material is low at high temperature, the high-pressure gas is easy to expand, after the temperature is reduced to room temperature, the air pressure is greatly reduced due to the increase of the air hole volume and the reduction of the temperature, the support of the air pressure is lost, and the foaming sole is greatly supported by the hardness of the material at the moment. The conventional EVA foaming light sole and the manufacturing process thereof have difficulty in considering the hardness support and high rebound resilience of the sole.
The physical properties of the EVA foaming sole material can be realized by adjusting the internal air pressure besides the physical properties of the matrix material, and the spring effect is realized by utilizing the compression-release energy of high-pressure air. According to pv=nrt, increasing the gas can increase the gas pressure at the same temperature and volume. In the operation of actual EVA foaming, under the condition of ensuring the same multiplying power, the air pressure can be increased by increasing the using amount of the foaming agent, under the conventional EVA secondary molding operation, the purpose of increasing the foaming agent can be achieved by increasing the crosslinking density or using an elastomer with larger Mooney viscosity, but the increasing amount is limited, and the poor processing fluidity of materials of the method is easy to cause the bad production of soles. The strength of the gas core wall is increased by cooling the die, high-pressure gas is not easy to expand at the moment of die opening, the integrity of the air holes can be kept, and the method can avoid the increase of the strength of the air holes by improving the crosslinking density, so that the fluidity of the material can be ensured, the range of elastomer raw material selection is larger, and the ratio of the elastomer raw material in the formula can be larger.
Disclosure of Invention
Based on the invention, the invention discloses an EVA chemical foaming sole material supported by air pressure and a preparation method thereof, which starts from an EVA chemical foaming secondary mould pressing process, improves the melt strength by utilizing temperature regulation and control, and simultaneously greatly increases the consumption of a foaming agent to enable the matrix strength to be matched with the air pressure when the EVA chemical foaming sole material is balanced, thereby improving the air pressure and enhancing the air in the sole.
The invention provides an EVA (ethylene-vinyl acetate) chemical foaming sole material supported by air pressure, which comprises the following components in parts by mass:
100 parts of EVA composite elastomer material; 5-10 parts of gas barrier rubber; 0.25 to 0.6 part of cross-linking agent; 6-10 parts of foaming agent; 0.25 to 0.5 part of stearic acid; 0.8 to 1.2 portions of zinc stearate; 1.2 to 2.5 parts of zinc oxide; 3-5 parts of filler.
Preferably, the EVA composite elastomer material is 40-60 parts of EVA; 40-60 parts of polyolefin elastomer; 0 to 20 parts of novel high-performance elastomer; wherein the VA mass content in EVA is 26-40%; the polyolefin elasticity comprises one or more of POE, OBCs, EPDM, SEBS and the like; the novel high-performance elastomer comprises one or more of thermoplastic polyurethane elastomer (TPU), polyester elastomer (TPEE), nylon elastomer (PEBA) and the like.
Preferably, the gas barrier rubber is butyl rubber or halogenated butyl rubber having outstanding air tightness.
Preferably, the crosslinker BIBP (1, 4-bis-tert-butylperoxy isopropyl benzene)
Preferably, the foaming agent is one or more of azodicarbonamide and modified foaming agent H.
Preferably, the filler is one or more of talc and calcium carbonate.
The invention provides a preparation method of an EVA chemical foaming sole supported by air pressure, which comprises the following specific steps:
step 1: weighing each composition according to the above-defined proportion, mixing all the weighed components except the cross-linking agent and the foaming agent, adding the weighed cross-linking agent and the foaming agent into the blended materials, continuously mixing, granulating the uniformly mixed mixture, and standing and cooling the manufactured particles.
Step 2: and (3) weighing particles in the step (1) according to the mould body, pouring the particles into a mould cavity, closing the mould, transferring the mould into a forming hot-pressing hole, automatically hooking the mould, locking the mould, performing hot-pressing foaming, and foaming for a certain time.
Step 3: and (3) transferring the die into a water cooling hole site, performing die pressing water cooling for a certain time, and opening the die to take out the air-filled cold blank.
Step 4: and (3) placing the air-filled cold blank in the step (3) in a transmission oven for heating and foaming to obtain the secondary molding small foam.
Step 5: and (3) performing secondary molding on the small molding foam in the step (3) to obtain the EVA chemical foaming sole material supported by air pressure.
Preferably, the banburying temperature in the step 1 is controlled to be 120-125 ℃, and the time for continuous banburying after adding the cross-linking agent and the foaming agent is 3-5 min.
Preferably, the automatic hook mold locking in the step 2 is a four-side hook, so as to increase the mold locking tightness and the mold locking force of the mold; the hot-pressing foaming is carried out at the temperature of 170-180 ℃ for 600-800 s.
Preferably, the water cooling time of the step 3 is 500-600 s.
Preferably, the parameters of the transmission oven in the step 4 are set as follows: temperature: one section of 90 ℃, two sections of 80 ℃, three sections of 70 ℃, four sections of 60 ℃; baking time: the whole process is 30-40 min.
Preferably, the secondary molding in the step 5 is carried out for 420-480 s, the water cooling time is 450-550 s, and the hot pressing temperature is 170-175 ℃.
Compared with the prior art, the invention has the beneficial effects that: the EVA chemical foaming sole material supported by air pressure adopts an improved secondary mould pressing process, a physical foaming temperature rising foaming method is used for reference, an air-filled cold blank is firstly prepared, then foaming is carried out outside a mould at a proper temperature, a temperature control means is adopted, the using amount of a foaming agent is increased, a conventional EVA chemical foaming sole formula is taken as a main part, gas barrier rubber is introduced, the air tightness is ensured, the air pressure in the material is improved, the prepared sole foaming material achieves the purpose of enhancing from the angle of air and not being limited to formula base material selection, and the ultra-light, ultra-elastic, soft and non-collapsing sole material can be developed, so that the static soft comfort and dynamic supporting stability of sports shoes are ensured. The physical properties of the sole can be compared with those of a supercritical physical foaming material, and the foaming process is greatly simplified compared with supercritical physical foaming.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an EVA (ethylene-vinyl acetate) chemical foaming sole material supported by air pressure, which comprises the following components in parts by mass:
100 parts of EVA composite elastomer material; 5-10 parts of gas barrier rubber; 0.25 to 0.6 part of cross-linking agent; 6-10 parts of foaming agent; 0.25 to 0.5 part of stearic acid; 0.8 to 1.2 portions of zinc stearate; 1.2 to 2.5 parts of zinc oxide; 3-5 parts of filler.
The EVA foaming sole material provided by the application improves the performance of the foaming material from the angle of enhancing the gas pressure, and the prepared foaming midsole material has ultra-light, ultra-elastic and soft without collapsing, ensures the static soft comfort and dynamic support stability of the sports shoes, can be comparable with high-performance physical foaming materials, and is used for high-performance training or racing shoes.
The material comprises 100 parts of EVA composite elastomer, wherein the EVA composite elastomer refers to a conventional formula which takes EVA as a main material, and is a composite polyolefin elastomer and a novel high-performance elastomer, and the polyolefin elastomer comprises one or more of POE, OBCs, EPDM, SEBS and the like and blending modified materials thereof; the novel high-performance elastomer comprises one or more of thermoplastic polyurethane elastomer (TPU), polyester elastomer (TPEE), nylon elastomer (PEBA) and the like. When the high-performance elastomer is introduced into the formula, the twin-screw is firstly adopted for melt blending.
Preferably, the EVA composite elastomer of the embodiment of the present application is in the following proportions by mass: 40-60 parts of EVA; 40-60 parts of polyolefin elastomer; 0 to 20 parts of novel high-performance elastomer. Specifically, in the EVA of the embodiment of the application, the VA content can be 26-40%, the molecular chain of the EVA with the VA content is high in flexibility, the softness and high rebound of the composite material are guaranteed, and the EVA can be one or more of EVA 7470M, EVA V33121 and EVA 40W, EVA L-03. Specifically, the polyolefin elastomer in the embodiment of the application is an EVA composite modified common elastomer, and has low crystallinity and good molecular chain flexibility, so that high rebound resilience performance is guaranteed, but the polyolefin elastomer has low hardness and small elastic modulus, and as the optimization, the polyolefin elastomer can be in the form of POE: engage 8180, engage 7467, engage 8150, engage 8003, OBCs Inuse 9107, inuse 9507, EPDM and SEBS blend modifiers NORDEL IP 3745P, EPT 3092M. The novel high-performance elastomer is a type of elastomer with rubber rebound resilience and engineering plastic strength, is widely used for physical foaming, has excellent rebound resilience and supporting stability, is prepared from thermoplastic polyurethane elastomer (TPU), polyester elastomer (TPEE) and nylon elastomer (PEBA), and has high melting temperature and softening point, and can improve the dimensional stability and rebound resilience of a foaming material by compounding the elastomer in an EVA formula, but because the high-temperature melt strength is low, the influence of high acidity on peroxide crosslinking in a system is large, the poor foaming is easily caused when the elastomer is introduced into the formula in a high proportion, and preferably, the component of the elastomer in the formula is not more than 20 parts, and the model of the elastomer is TPU: elastollan 1190A; TPEE Hytrel 4056, G-4065D, H-4865D, PEBA VESTAMID E-S3, pebax 4033. The composite foaming material can ensure the comprehensive performance of the composite foaming material through reasonable formula proportion.
The material comprises 5-10 parts of gas barrier rubber, wherein the gas barrier rubber is butyl rubber or halogenated butyl rubber, the butyl rubber is a copolymer of butene and a small amount of isoprene, an isobutylene main chain is a main component of the butyl rubber, symmetrical methyl groups on two sides of the butyl rubber lead to steric hindrance, so that a rubber molecular chain moves slowly, gas molecules are difficult to pass through, the effect of increasing air tightness is achieved, the butyl rubber has excellent air tightness, but the molecular chain has poor flexibility and poor rebound resilience, and the air tightness of the composite foaming material can be improved to achieve the purpose of pressure maintaining by introducing the composite foaming material into an EVA formula in a reasonable component, and meanwhile, the high rebound resilience of the composite foaming material is ensured. In the examples of the present application, preferably, the butyl rubber type selected is BIIR X2, mooney viscosity 46[ ML (1+8) 125 ℃).
The material comprises 6-10 parts of foaming agent, wherein the foaming agent is one or more of azodicarbonamide and modified foaming agent H. The azodicarbonamide is used as a foaming agent, so that the foaming is rapid and stable, the gas generation amount is large, and no residue exists. Specifically, as examples of the present application, the azodicarbonamide blowing agent was selected to have a small particle size, a narrow distribution, and a particle size in the range of 5 to 10 μm. The fine particle size ensures that the foaming agent is distributed more uniformly in the composite matrix material, can ensure more gas nuclei formed during foaming, has small cell size and large cell density, and the narrow distribution can ensure the uniformity of air holes. The foaming agent H is N, N-dinitroso pentamethylene tetramine, the decomposition amount is large, the ammonia amount in the decomposition product is more than that of other foaming agents, but the decomposition temperature is higher, urea is used as an auxiliary foaming agent, the decomposition temperature can be reduced to be lower than 140 ℃, for some EVA composite base materials with stronger acidity (such as thermoplastic polyurethane elastomer (TPU), polyester elastomer (TPEE) and nylon elastomer (PEBA) introduced into a formula, the acidity is generally higher), the base material acid property influences the peroxide free radical decomposed by the bridging agent to influence the crosslinking reaction of the system, and the ammonia generated by the decomposition of the modified foaming agent H can regulate the acidity of the system before the peroxide bridging agent is decomposed by adding the urea modified foaming agent H, so that the system foams normally to achieve the aim of introducing the high-performance elastomer. In the embodiment of the present application, preferably, the blowing agent type is: azodicarbonamide is AC6000 or AC7000, and modified foaming agent H is S12.
According to pv=nrt, increasing the gas can increase the gas pressure at the same temperature and volume. In the operation of actual EVA foaming, the air pressure can be increased by increasing the consumption of the foaming agent under the condition of ensuring the same multiplying power. However, with the increase of the foaming agent, the air pressure is increased, and when the strength of the cell wall cannot bind the air, the air holes are broken, and the performance of the foaming material is reduced. In the examples of the present application, the blowing agent is used in an amount of 6 to 10 parts, preferably 7 to 8 parts.
The material comprises 3-5 parts of filler, which is also called filler, additive and filler, and can improve the material performance and reduce the cost. In the present application, the filler is preferably one or more selected from talc and calcium carbonate, and more preferably talc. In the preferred embodiment of the invention, the filler is uniformly and finely divided particles with the particle size smaller than 6 mu m, and can be well and uniformly distributed in the whole composite material system to play a role of heterogeneous nucleation, so that the foaming cells are more uniform.
Stearic acid, zinc stearate and zinc oxide in the materials are conventional foaming aids, and the materials are commercially available without specific requirements.
Correspondingly, the invention provides a preparation method of the EVA chemical foaming sole supported by air pressure, which comprises the following steps:
step 1: weighing each composition according to the above-defined proportion, mixing all the weighed components except the cross-linking agent and the foaming agent, adding the weighed cross-linking agent and the foaming agent when mixing the blended materials, granulating the uniformly mixed mixture, and placing and cooling the manufactured particles.
Step 2: and (3) weighing particles in the step (1) according to the mould body, pouring the particles into a mould cavity, closing the mould, transferring the mould into a forming hot-pressing hole, and automatically hooking and locking the mould to perform hot-pressing foaming.
Step 3: and (3) transferring the die into a water cooling hole site, performing die pressing water cooling for a certain time, and opening the die to take out the air-filled cold blank.
Step 4: and (3) heating and foaming the air-filled cold blank in the step (3) in a transmission oven to obtain the secondary molding small foam.
Step 5: and (3) performing secondary compression molding on the molding small foam in the step (4) to obtain the EVA chemical foaming sole material supported by air pressure.
According to the preparation method, the traditional processing mode of the secondary MD foaming sole material is used for referencing the concept of supercritical physical foaming and heating foaming, the foaming is performed by low-temperature foaming by using a heating means while the gas quantity is increased through temperature control, the strength of cells is improved, the gas pressure and the strength of the cells are balanced, and therefore the gas pressure of the foaming material is enhanced.
In the step 1 of the application, mixing all the weighed components except the cross-linking agent and the foaming agent, wherein the mixing temperature is controlled to be 120-125 ℃, the continuous mixing time is 3-5 min after the cross-linking agent and the foaming agent are added, the mixing temperature ensures the uniform mixing of all materials, and the continuous mixing time ensures the uniform mixing of the bridging agent without decomposing to cause dead materials;
in the step 2, the automatic hook is a conventional component of an MD secondary foaming forming die, and the conventional single-side hook is improved into a four-side hook, so that the die clamping tightness and the die clamping force of the die are improved, and the defects of material overflow in a die cavity due to strong expansion air pressure, edge burst and the like can be limited; the hot-pressing foaming is carried out in a way that the temperature of a hot-pressing plate is 170-180 ℃ and the hot-pressing time is 600-800 s;
after the molded water is cooled for a certain time in the step 3, the mold is opened to take out an air-filled cold blank, wherein the water cooling time is 500-600 s, the air-filled cold blank is a micro-foaming cold blank, the foaming multiplying power is 1.05-1.2 (the multiplying power line length of the air-filled cold blank/the multiplying power line length of a mold), an air core is formed in the air-filled cold blank, the air pressure is relatively low at a low temperature, a base material is far lower than the softening point temperature, a chain segment is not easy to move, the base strength is high, and the growth expansion of air holes is limited.
In the step 4 of the application, the inflatable cold blank is heated and foamed in a transmission oven to obtain secondary molding small foam, wherein the heating and foaming are performed in the transmission oven in a manner that the parameters of the transmission oven are set as follows: temperature: one section of 90 ℃, two sections of 80 ℃, three sections of 70 ℃, four sections of 60 ℃; baking time: the whole process is controlled by the transmission rotating speed for 30-40 min; the secondary molding small foaming multiplying power is 1.9-2.1. When the oven is heated, the gas pressure is enhanced along with the temperature rise, the activity capacity of the molecular chain segments of the matrix is increased, and in order to achieve the balance of the gas pressure and the strength of the air holes, the air holes grow and expand to complete foaming, so that the foaming material is ensured to be completely foamed when reaching the bonding process of the shoe material at the temperature, and the foaming material cannot be expanded again to cause bad effect when being irradiated in the bonding process.
Compared with the conventional foaming (the mold opening temperature is 170-180 ℃), the strength of the foam cells at low temperature (70-90 ℃) is high, the influence of the pressure drop of the gas pressure caused by the temperature on the deformation of the foam cells is small when the gas pressure is cooled to the room temperature, the influence of the pressure drop caused by the temperature on the volume increase of the foam cells is small when the gas pressure is balanced with the strength of the foam cells, and the gas pressure is increased by the strength of the foam cells, so that the pressure increase is achieved. From the appearance, the blowing agent amount of the present application is larger (6 to 10 parts) than the conventional blowing agent amount (3 to 6 parts) at the same magnification (magnification of 2.0), and the gas pressure in the small foam material is high according to pv=nrt.
Step 4 of the method is carried out according to conventional mould pressing, the hot pressing time is usually 420-480 s, the water cooling time is 450-550 s, and the hot pressing temperature is 170-175 ℃.
For further explanation of the present application, the EVA chemical foaming sole material providing pneumatic support of the present application and the method of preparing the same are described in detail below with reference to examples, but they should not be construed as limiting the scope of protection of the present application.
Example 1
The EVA chemical foaming sole material supported by air pressure comprises the following components in parts by mass:
100 parts of EVA composite elastomer material; 5 parts of gas barrier rubber; 0.42 parts of a crosslinking agent; 7.8 parts of a foaming agent; 0.5 parts of stearic acid; 1 part of zinc stearate; 1.5 parts of zinc oxide; 3.3 parts of filler.
Wherein 100 parts of EVA composite elastomer consists of 50 parts of EVA V33121, 45 parts of POE Engage 8003 and 5 parts of EPDM NORDEL IP 3745P, wherein EVA V33121 is produced by Taiwan polymerization, and POE Engage 8003 and EPDM NORDEL IP 3745P are produced by America Dow; the gas barrier rubber is brominated butyl rubber, and the brand X2 is produced by Langsheng Germany; the cross-linking agent is BIBP (di-tert-butyl-peroxide diisopropylbenzene), manufactured by Guangzhou Fang Rui; the foaming agent is azodicarbonamide, which is produced by new Fujian jin Lang materials with the brand of AC 6000; the filler is talcum powder produced by Xufeng company.
The preparation method of the EVA chemical foaming sole supported by air pressure comprises the following steps of:
step 1: weighing each composition according to the defined proportion, mixing all the weighed components except the cross-linking agent and the foaming agent, turning the materials for 4-5 times, controlling the banburying temperature to be 120-125 ℃, adding the weighed cross-linking agent and the foaming agent when mixing the blended materials, continuing mixing for 3-5 min, granulating the uniformly mixed mixture, and placing and cooling the manufactured particles;
step 2: and (2) weighing particles in the step (1) according to a mold body, pouring the particles into a mold cavity, closing the mold, transferring the mold into a molding hot-pressing hole, automatically hooking and locking the mold, performing hot-pressing foaming, performing hot pressing for 600s, performing hot pressing at 165-175 ℃,
step 3: transferring the mold into a water cooling hole site, molding water for 600s, opening the mold, taking out the air-filled cold blank, and multiplying power is about 1.1;
step 4: heating and foaming the air-filled cold blank in the step 3 in a transmission oven, and baking for 30-33 min in the whole process to obtain secondary molding small foam with the multiplying power of about 2.07;
step 5: and (3) performing secondary compression molding on the molding small foam in the step (4), wherein the constant hot-pressing time is 450s, and the water cooling time is 500s, so as to obtain the EVA chemical foaming sole material supported by air pressure.
Example 2
The EVA chemical foaming sole material supported by air pressure comprises the following components in parts by mass:
100 parts of EVA composite elastomer material; 5 parts of gas barrier rubber; 0.45 parts of a crosslinking agent; 8 parts of a foaming agent; 0.5 parts of stearic acid; 1 part of zinc stearate; 1.5 parts of zinc oxide; 3.3 parts of filler.
Wherein 100 parts of EVA composite elastomer consists of 45 parts of EVA 7470M, 25 parts of POE Engage 8150, 20 parts of OBCs INFUSE 9507 and 10 parts of EPDM EPT 3092M, wherein EVA 7470M is produced by Taiwan plastic in China, POE Engage 8150 and OBCs INFUSE 9507 are produced by Dow in the United states, and EPDM EPT 3092M is produced by Mitsui chemical in Japan; the gas barrier rubber is brominated butyl rubber, and the brand X2 is produced by Langsheng Germany; the cross-linking agent is BIBP (di-tert-butyl-peroxide diisopropylbenzene), manufactured by Guangzhou Fang Rui; the foaming agent is azodicarbonamide, which is produced by new Fujian jin Lang materials with the brand of AC 6000; the filler is talcum powder produced by Xufeng company.
The preparation method of the EVA chemical foaming sole material supported by air pressure comprises the following steps of:
step 1: weighing each composition according to the defined proportion, mixing all the weighed components except the cross-linking agent and the foaming agent, turning the materials for 4-5 times, controlling the banburying temperature to be 120-125 ℃, adding the weighed cross-linking agent and the foaming agent when mixing the blended materials, continuing mixing for 3-5 min, granulating the uniformly mixed mixture, and placing and cooling the manufactured particles.
Step 2: and (2) weighing particles in the step (1) according to a mold body, pouring the particles into a mold cavity, closing the mold, transferring the mold into a molding hot-pressing hole, automatically hooking and locking the mold, performing hot-pressing foaming, performing hot pressing for 600s, performing hot pressing at 165-175 ℃,
step 3: transferring the mold into a water cooling hole site, molding water for 600s, opening the mold, taking out the air-filled cold blank, and multiplying power is about 1.15;
step 4: heating and foaming the air-filled cold blank in the step 3 in a transmission oven, and baking for 30-33 min in the whole process to obtain secondary molding small foam with the multiplying power of about 1.96;
step 5: and (3) performing secondary compression molding on the molding small foam in the step (4), and performing constant hot-pressing for 480s and water cooling for 500s to obtain the EVA chemical foaming sole material supported by air pressure.
Example 3
The EVA chemical foaming sole material supported by air pressure comprises the following components in parts by mass:
100 parts of EVA composite elastomer material; 10 parts of gas barrier rubber; 0.5 parts of cross-linking agent and 9 parts of foaming agent; 0.5 parts of stearic acid; 1 part of zinc stearate; 2 parts of zinc oxide; 3.3 parts of filler.
Wherein 100 parts of EVA composite elastomer consists of 40 parts of EVA V33121, 10 parts of POE Inuse 9107, 25 parts of POE Engage 8003, 20 parts of TPEE Hytrel No. 4056 and 5 parts of EPDM NORDEL IP 3745P, wherein EVA V33121 is produced by Taiwan sub-polymerization, POE Engage 8003, inuse 9107 and EPDM NORDEL IP 3745P are produced by the United states ceramic, TPEE Hytrel No. 4056 is produced by DuPont company, and the EVA composite elastomer of the components is prepared by double-screw melt blending; the gas barrier rubber is brominated butyl rubber, and the brand X2 is produced by Langsheng Germany; the cross-linking agent is BIBP (di-tert-butyl-peroxide diisopropylbenzene), manufactured by Guangzhou Fang Rui; 7 parts of azodicarbonamide and 2 parts of modified H foaming agent, wherein the azodicarbonamide is AC6000, and the modified H foaming agent is S12, which are produced by using new Fujian jin Lang materials; the filler is talcum powder produced by Xufeng company.
The preparation method of the EVA chemical foaming sole material supported by air pressure comprises the following steps of:
step 1: weighing each composition according to the defined proportion, mixing all the weighed components except the cross-linking agent and the foaming agent, turning the materials for 4-5 times, controlling the banburying temperature to be 120-125 ℃, adding the weighed cross-linking agent and the foaming agent when mixing the blended materials, continuing mixing for 3-5 min, granulating the uniformly mixed mixture, and placing and cooling the manufactured particles.
Step 2: and (3) weighing particles in the step (1) according to a certain mass of a mold body, pouring the particles into a mold cavity, closing the mold, transferring the mold into a molding hot-pressing hole, automatically hooking the mold, locking the mold, performing hot-pressing foaming, and performing hot-pressing for 700 seconds, wherein the hot-pressing temperature is 165-175 ℃.
Step 3: and (3) transferring the die into a water cooling hole site, performing die pressing water cooling for 600s, opening the die, and taking out the air-filled cold blank, wherein the multiplying power is about 1.06.
Step 4: and (3) heating and foaming the air-filled cold blank in the step (3) in a transmission oven, and baking for 30-33 min in the whole process to obtain the secondary molding small foam with the multiplying power of about 2.05.
Step 5: and (3) performing secondary compression molding on the molding small foam in the step (4), and performing constant hot pressing for 420s and water cooling for 500s to obtain the EVA chemical foaming sole material supported by air pressure.
Example 4
The EVA chemical foaming sole material supported by air pressure comprises the following components in parts by mass:
100 parts of EVA composite elastomer material; 10 parts of gas barrier rubber; 0.5 parts of cross-linking agent and 9 parts of foaming agent; 0.5 parts of stearic acid; 1 part of zinc stearate; 2 parts of zinc oxide; 3.3 parts of filler.
Wherein 100 parts of EVA composite elastomer consists of 40 parts of EVA V33121, 10 parts of POE Inuse 9507, 25 parts of POE Engage 8150, 20 parts of Pebax 4033 and 5 parts of EPDM NORDEL IP 3745P, wherein EVA V33121 is produced by Taiwan sub-polymerization, POE Engage 8003, inuse 9107 and EPDM NORDEL IP 3745P are produced by America Dow, pebax 4033 is produced by French Achroma, and the EVA composite elastomer of the components is prepared by double-screw melt blending; the gas barrier rubber is brominated butyl rubber, and the brand X2 is produced by Langsheng Germany; the cross-linking agent is BIBP (di-tert-butyl-peroxide diisopropylbenzene), manufactured by Guangzhou Fang Rui; 7 parts of azodicarbonamide and 2 parts of modified H foaming agent, wherein the azodicarbonamide is AC6000, and the modified H foaming agent is S12, which are produced by using new Fujian jin Lang materials; the filler is talcum powder produced by Xufeng company.
The preparation method of the EVA chemical foaming sole material supported by air pressure comprises the following steps of:
step 1: weighing each composition according to the defined proportion, mixing all the weighed components except the cross-linking agent and the foaming agent, turning the materials for 4-5 times, controlling the banburying temperature to be 120-125 ℃, adding the weighed cross-linking agent and the foaming agent when mixing the blended materials, continuing mixing for 3-5 min, granulating the uniformly mixed mixture, and placing and cooling the manufactured particles.
Step 2: and (3) weighing particles in the step (1) according to a certain mass of a mold body, pouring the particles into a mold cavity, closing the mold, transferring the mold into a molding hot-pressing hole, automatically hooking the mold, locking the mold, performing hot-pressing foaming, and performing hot-pressing for 700 seconds, wherein the hot-pressing temperature is 165-175 ℃.
Step 3: and (3) transferring the die into a water cooling hole site, performing die pressing water cooling for 600s, opening the die, and taking out the air-filled cold blank, wherein the multiplying power is about 1.1.
Step 4: and (3) heating and foaming the air-filled cold blank in the step (3) in a transmission oven, and baking for 30-33 min in the whole process to obtain the secondary molding small foam with the multiplying power of about 2.1.
Step 5: and (3) performing secondary compression molding on the molding small foam in the step (4), and performing constant hot pressing for 420s and water cooling for 500s to obtain the EVA chemical foaming sole material supported by air pressure.
Comparative example 1
The formula of the light EVA chemical foaming sole material is as follows:
100 parts of EVA composite elastomer material; 5 parts of gas barrier rubber; 0.5 parts of cross-linking agent and 5.5 parts of foaming agent; 0.5 parts of stearic acid; 1 part of zinc stearate; 1.5 parts of zinc oxide; 3.3 parts of filler.
Wherein 100 parts of EVA composite elastomer consists of 50 parts of EVA V33121, 45 parts of POE Engage 8003 and 5 parts of EPDM NORDEL IP 3745P, wherein EVA V33121 is produced by Taiwan polymerization, and POE Engage 8003 and EPDM NORDEL IP 3745P are produced by America Dow; the gas barrier rubber is brominated butyl rubber, and the brand X2 is produced by Langsheng Germany; the cross-linking agent is BIBP (di-tert-butyl-peroxide diisopropylbenzene), manufactured by Guangzhou Fang Rui; the foaming agent is azodicarbonamide, which is produced by new Fujian jin Lang materials with the brand of AC 6000; the filler is talcum powder produced by Xufeng company.
A preparation method of a light EVA foaming sole material comprises the following steps:
step 1: weighing each composition according to the defined proportion, mixing all the weighed components except the cross-linking agent and the foaming agent, turning the materials for 4-5 times, controlling the banburying temperature to be 120-125 ℃, adding the weighed cross-linking agent and the foaming agent when mixing the blended materials, continuing mixing for 3-5 min, granulating the uniformly mixed mixture, and placing and cooling the manufactured particles.
Step 2: and (3) carrying out small foaming on the particles in the step (1), wherein the mold temperature is about 165-175 ℃, and the vulcanizing time is about 600 seconds, so that a small foaming coarse embryo is obtained, and the multiplying power is about 2.05.
Step 3: and (3) performing secondary compression molding on the molding small foam in the step (2), wherein the hot pressing time is 450s, and the water cooling time is 500s, so as to obtain the light EVA chemical foaming sole material.
Comparative example 2
The light EVA foaming sole material comprises the following components in parts by mass:
100 parts of EVA composite elastomer material; 10 parts of gas barrier rubber; 0.5 parts of cross-linking agent and 6 parts of foaming agent; 0.5 parts of stearic acid; 1 part of zinc stearate; 2 parts of zinc oxide; 3.3 parts of filler.
Wherein 100 parts of EVA composite elastomer consists of 40 parts of EVA V33121, 10 parts of POE Inuse 9107, 25 parts of POE Engage 8003, 20 parts of TPEE Hytrel No. 4056 and 5 parts of EPDM NORDEL IP 3745P, wherein EVA V33121 is produced by Taiwan sub-polymerization, POE Engage 8003, inuse 9107 and EPDM NORDEL IP 3745P are produced by the United states ceramic, TPEE Hytrel No. 4056 is produced by DuPont company, and the EVA composite elastomer of the components is prepared by double-screw melt blending; the gas barrier rubber is brominated butyl rubber, and the brand X2 is produced by Langsheng Germany; the cross-linking agent is BIBP (di-tert-butyl-peroxide diisopropylbenzene), manufactured by Guangzhou Fang Rui; the foaming agent is 4.5 parts of azodicarbonamide and 1.5 parts of modified H foaming agent, wherein the azodicarbonamide is AC6000, and the modified H foaming agent is S12, which are produced by using the new Fujian Kong wave material; the filler is talcum powder produced by Xufeng company.
A preparation method of a light EVA foaming sole material comprises the following steps:
step 1: weighing each composition according to the defined proportion, mixing all the weighed components except the cross-linking agent and the foaming agent, turning the materials for 4-5 times, controlling the banburying temperature to be 120-125 ℃, adding the weighed cross-linking agent and the foaming agent when mixing the blended materials, continuing mixing for 3-5 min, granulating the uniformly mixed mixture, and placing and cooling the manufactured particles;
step 2: and (3) carrying out small foaming on the particles in the step (1), wherein the mold temperature is about 165-175 ℃, and the vulcanizing time is about 600 seconds, so that a small foaming coarse embryo is obtained, and the multiplying power is about 2.05.
Step 3: and (3) performing secondary compression molding on the molding small foam in the step (2), wherein the hot pressing time is 420s, and the water cooling time is 500s, so as to obtain the light EVA chemical foaming sole material.
Comparative example 3
The formula of the light EVA chemical foaming sole material is as follows:
100 parts of EVA composite elastomer material; 10 parts of gas barrier rubber; 0.5 parts of cross-linking agent and 5.8 parts of foaming agent; 0.5 parts of stearic acid; 1 part of zinc stearate; 1.5 parts of zinc oxide; 3.3 parts of filler.
Wherein, 100 parts of EVA composite elastomer consists of 30 parts of EVA 7350M, 20 parts of EVA 7470M,30 parts of POE Engage 8003, 15 parts of POE Engage 8450 and 5 parts of EPDM NORDEL IP 3745P, wherein, EVA 7350M and 7470M are produced by Taiwan platform plastic, POE Engage 8003, POE Engage 8450 and EPDM NORDEL IP 3745P are produced by America Dow; the cross-linking agent is BIBP (di-tert-butyl-peroxide diisopropylbenzene), manufactured by Guangzhou Fang Rui; the foaming agent is azodicarbonamide AC6000, and is produced by new Fujian Kong wave materials; the filler is talcum powder produced by Xufeng company.
A preparation method of a light EVA foaming sole material comprises the following steps:
step 1: weighing each composition according to the defined proportion, mixing all the weighed components except the cross-linking agent and the foaming agent, turning the materials for 4-5 times, controlling the banburying temperature to be 120-125 ℃, adding the weighed cross-linking agent and the foaming agent when mixing the blended materials, continuing mixing for 3-5 min, granulating the uniformly mixed mixture, and placing and cooling the manufactured particles;
step 2: and (3) carrying out small foaming on the particles in the step (1), wherein the mold temperature is about 165-175 ℃, and the vulcanizing time is about 600 seconds, so that a small foaming coarse embryo is obtained, and the multiplying power is about 2.05.
Step 3: and (3) performing secondary compression molding on the molding small foam in the step (2), wherein the hot pressing time is 420s, and the water cooling time is 500s, so as to obtain the light EVA chemical foaming sole material.
The EVA foaming materials prepared in the examples and the comparative examples are subjected to physical property test, and the results are shown in Table 1:
table 1 results of performance test of EVA foam of examples and comparative examples
Remarks:
test method of compression average modulus (reference: reciprocating compression Performance of elastomer foam and life prediction thereof): the weight of the middle body is 75Kg as the best reference object, and the acting force of the sportsman on the middle sole is about 2 times of the gravity of the sportsman during running, so that the maximum axial pressure of the experimental test is 1500N. The running and foot falling time and the take-off time are about 0.1s, the stress of the midsole is from 0 to 1500N to 0, and the emptying time is about 0.51s. The sample was subjected to a reciprocating compression fatigue test at a maximum load of 1500N and a frequency of 1.41Hz. The force-time of reciprocating compression is set to be 0 in 0-1500N in 0-0.1 s time, 0 in 1500N in 0.1-0.2 s time and 0 in 0,0.2-0.71 s time, the value of the load-displacement curve is averaged to obtain the average value of the similar data, and the reciprocating compression is carried out 200 times in the application, 190 times is obtained th 、195 th 、200 th Average of three sets of compression modulus.
The stability of the midsole is generally related to its stiffness, which is high to ensure midsole support stability, and is generally determined by the base hardness and density of the foam material. In order to obtain higher resilience performance, the base material is usually selected to have a relatively low hardness, which results in a low hardness, and it is difficult to secure the support stability (as in comparative example 1). In order to achieve the effect of supporting stability at the same time, a high-performance elastomer is required to be introduced into the formula, and too great change of hardness support (such as comparative example 2) is difficult to cause due to the problems of limited addition amount and chemical foaming process. If the sole formulation selects a base material with high hardness for ensuring the support stability, the rebound performance of the foaming material is poor (as in comparative example 3) due to the problem of the chemical foaming process. The traditional chemical foaming formula and the traditional chemical foaming process are difficult to achieve both supporting stability and rebound performance.
In the embodiments 1 to 4, from the angle of air pressure enhancement of the inflatable material, the air pressure of the midsole material is increased by means of increasing the foaming agent and controlling the temperature, so that the compression average modulus of the midsole material is greatly improved, and under the relatively low hardness, the higher average compression modulus is obtained, so that the supporting stability of the midsole material is ensured, the selection range of the formula base material is greatly widened, the requirement of high rebound resilience performance of the midsole material can be met, and meanwhile, the density of the midsole material is further reduced by increasing the air pressure, so that the rebound resilience performance of the midsole material is improved (the embodiments 1 and 3 and the comparative examples 1 and 2).
In summary, the EVA foaming material supported by air pressure prepared by the method has excellent performance: the density is 0.08-0.09 g/cm < 3 >, the hardness is 40-43 ℃ and the rebound is 69-78%, the performance can be comparable with that of the supercritical physical foaming shoe material, and the process is greatly simplified compared with that of the supercritical physical foaming shoe material.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The EVA chemical foaming sole material supported by air pressure comprises the following components in parts by mass:
100 parts of EVA composite elastomer material; 5-10 parts of gas barrier rubber; 0.25 to 0.6 part of cross-linking agent; 6-10 parts of foaming agent; 0.25 to 0.5 part of stearic acid; 0.8 to 1.2 portions of zinc stearate; 1.2 to 2.5 parts of zinc oxide; 3-5 parts of filler;
the EVA composite elastomer material is 40-60 parts of EVA; 40-60 parts of polyolefin elastomer; 0 to 20 parts of novel high-performance elastomer.
2. The air pressure supported EVA chemical foaming sole material as claimed in claim 1, wherein the EVA has a VA mass content of 26-40%; the polyolefin elasticity comprises one or more of POE, OBCs, EPDM, SEBS and the like; the novel high-performance elastomer comprises one or more of thermoplastic polyurethane elastomer (TPU), polyester elastomer (TPEE), nylon elastomer (PEBA) and the like.
3. An EVA chemical foaming sole material supported by air pressure as claimed in claim 1, wherein the gas barrier rubber is butyl rubber or halogenated butyl rubber with outstanding air tightness; the crosslinking agent BIBP (1, 4-di-tert-butyl peroxyisopropyl benzene).
4. An air pressure supported EVA chemically foamed sole material according to claim 1, wherein the foaming agent is one or more of azodicarbonamide and modified foaming agent H; the filler is one or more of talcum powder and calcium carbonate.
5. A method of making a pneumatically-supported EVA chemically foamed sole of any one of claims 1-4, comprising the steps of:
step 1: weighing each composition according to a defined proportion, mixing all the weighed components except the cross-linking agent and the foaming agent, adding the weighed cross-linking agent and the foaming agent when mixing the blended materials, granulating the uniformly mixed mixture, and placing and cooling the manufactured particles;
step 2: weighing particles in the step 1 according to a mold body, pouring the particles into a mold cavity, closing the mold, transferring the mold into a molding hot-pressing hole, automatically hooking the mold, locking the mold, and performing hot-pressing foaming;
step 3: transferring the mold into a water cooling hole site, performing mold pressing water cooling for a certain time, and opening the mold to take out an air-filled cold blank;
step 4: heating and foaming the air-filled cold blank in the step 3 in a transmission oven to obtain secondary molding small foaming;
step 5: and (3) performing secondary compression molding on the molding small foam in the step (4) to obtain the EVA chemical foaming sole material supported by air pressure.
6. The method for preparing a pneumatically supported EVA chemically foamed sole of claim 5, wherein the automatic hook mold locking of the step is a four-sided hook to increase the mold closing tightness and mold locking force of the mold; the hot-pressing foaming is carried out at the temperature of 170-180 ℃ for 600-800 s.
7. The method for preparing a pneumatically-supported EVA chemical foaming shoe sole as claimed in claim 5, wherein the water cooling time in the step 3 is 500-600 s.
8. The method for preparing an EVA chemical foaming sole supported by air pressure according to claim 5, wherein the parameters of the transmission oven in the step 4 are set as follows: temperature: one section of 90 ℃, two sections of 80 ℃, three sections of 70 ℃, four sections of 60 ℃; baking time: the whole process is 30-40 min.
9. The method for preparing an EVA chemical foaming sole supported by air pressure as claimed in claim 5, wherein the secondary molding in the step 5 is carried out for 420-480 s, the water cooling time is 450-550 s, and the hot pressing temperature is 170-175 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311460908.6A CN117534895A (en) | 2023-11-06 | 2023-11-06 | Air pressure supported EVA (ethylene-vinyl acetate) chemical foaming sole material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311460908.6A CN117534895A (en) | 2023-11-06 | 2023-11-06 | Air pressure supported EVA (ethylene-vinyl acetate) chemical foaming sole material and preparation method thereof |
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