CN111849058A - EVA/TPEE supercritical foaming composite shoe material and preparation method thereof - Google Patents
EVA/TPEE supercritical foaming composite shoe material and preparation method thereof Download PDFInfo
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- CN111849058A CN111849058A CN202010684615.6A CN202010684615A CN111849058A CN 111849058 A CN111849058 A CN 111849058A CN 202010684615 A CN202010684615 A CN 202010684615A CN 111849058 A CN111849058 A CN 111849058A
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- 229920006346 thermoplastic polyester elastomer Polymers 0.000 title claims abstract description 132
- 238000005187 foaming Methods 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 120
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 120
- -1 polyethylene maleic anhydride copolymer Polymers 0.000 claims abstract description 53
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 53
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 43
- 229920000570 polyether Polymers 0.000 claims abstract description 43
- 239000002667 nucleating agent Substances 0.000 claims abstract description 42
- 150000002978 peroxides Chemical class 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 51
- 238000012360 testing method Methods 0.000 claims description 36
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 238000005520 cutting process Methods 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 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
- 238000000034 method Methods 0.000 claims description 5
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000006260 foam Substances 0.000 abstract description 3
- DEKVAWHRMRNKMI-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3-propan-2-ylbenzene Chemical group CC(C)C1=CC=CC(OOC(C)(C)C)=C1OOC(C)(C)C DEKVAWHRMRNKMI-UHFFFAOYSA-N 0.000 description 13
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 13
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 13
- 239000002202 Polyethylene glycol Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/10—Footwear characterised by the material made of 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
- 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
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
- C08J9/008—Nanoparticles
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- 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
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- 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
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
Abstract
The invention belongs to the technical field of shoe products, and particularly relates to an EVA/TPEE supercritical foaming composite shoe material and a preparation method thereof. The EVA/TPEE supercritical foaming composite shoe material comprises the following preparation raw materials in parts by weight: 30-40 parts of ethylene-vinyl acetate copolymer, 30-40 parts of thermoplastic polyester elastomer, 10-20 parts of styrene-butadiene block copolymer, 5-8 parts of polyether grafted polyethylene maleic anhydride copolymer, 1-3 parts of peroxide and 1.2-1.6 parts of nucleating agent. The EVA/TPEE supercritical foaming composite material disclosed by the invention has the advantages of good foaming effect, high foaming efficiency, uniform, small and compact foam holes, difficulty in generating macropore and open pore phenomena during foaming, excellent mechanical properties and service performance such as light weight, high strength and the like, high tensile strength, large elongation at break, good mechanical properties, extremely high tear resistance strength and rebound rate, improvement on the blending uniformity of the EVA/TPEE, and low mass wear rate of the material for supercritical foaming composite shoes.
Description
Technical Field
The invention belongs to the technical field of shoe products, and particularly relates to an EVA/TPEE supercritical foaming composite shoe material and a preparation method thereof.
Background
The EVA chemical foaming material is a conventional foaming material in the application aspect of the current shoe material, has soft texture, is comfortable and light, has good anti-slip effect, has mechanical strength and resilience performance which can meet the requirements of common shoe materials, and is accepted by consumers, but along with the social development, people have higher and higher requirements on the environment protection and the smell of shoes, and the chemical foaming EVA has the problems that the foaming agent residue is not friendly to the environment and has slight smell because the foaming agent is not uniformly mixed, so the foaming is not uniform, the quality is not influenced and the like.
Thermoplastic polyester elastomer (TPEE) is a linear block copolymer containing hard polyester segment and soft aliphatic polyester or polyether segment, and has both excellent elasticity of rubber and easy processability of thermoplastic plastics, and recently, foamed materials are increasingly used in shoe materials. TPEE has low melt strength, and is easy to generate phenomena of macropore, open pore or uneven pore diameter during foaming, thereby limiting the application of the TPEE in the aspect. At present, EVA/TPEE blending has uneven risk, is difficult to reach the uniformity of molecular level, and brings adverse effect to the uniformity of foaming cells.
Disclosure of Invention
In order to solve the technical problems, the invention provides a material for EVA/TPEE supercritical foaming composite shoes, which is prepared from the following raw materials in parts by weight: 30-40 parts of ethylene-vinyl acetate copolymer, 30-40 parts of thermoplastic polyester elastomer, 10-20 parts of styrene-butadiene block copolymer, 5-8 parts of polyether grafted polyethylene maleic anhydride copolymer, 1-3 parts of peroxide and 1.2-1.6 parts of nucleating agent.
As a preferred technical scheme, the melt mass flow rate of the ethylene-vinyl acetate copolymer is 2.5-4g/10 min.
As a preferable technical scheme, the Shore D hardness of the thermoplastic polyester elastomer is 40-63.
As a preferred technical scheme, the density of the thermoplastic polyester elastomer is 1.15-1.23g/cm3。
As a preferred embodiment, the styrene-butadiene block copolymer is a linear styrene-butadiene block copolymer.
As a preferred technical solution, the peroxide is an organic peroxide.
As a preferable technical scheme, the nucleating agent is selected from one or more of nano zinc oxide, nano montmorillonite, nano titanium dioxide, nano calcium carbonate and nano white carbon black.
As a preferable technical scheme, the raw material for preparing the EVA/TPEE supercritical foaming composite shoe material also comprises 1-3 parts by weight of zinc stearate.
The invention provides a preparation method of an EVA/TPEE supercritical foaming composite shoe material, which at least comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, thermoplastic polyester elastomer, styrene-butadiene block copolymer, nucleating agent, polyether grafted polyethylene maleic anhydride copolymer and zinc stearate, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) and cutting a size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out a pressure relief test piece after gas saturation, and cutting the sample to obtain the EVA/TPEE supercritical foaming composite shoe material.
As a preferred technical scheme, the gas is supercritical N2(ii) a Of the foaming kettleThe pressure is 12-15 MPa; the temperature of the foaming kettle is 135-145 ℃; the gas saturation time is 4-6 h; the pressure relief time is 10-20 s.
Has the advantages that: the EVA/TPEE supercritical foaming composite shoe material provided by the invention has uniform pore size distribution, no open pore or combined pore, remarkably improved rebound rate, remarkably reduced mass wear rate, improved compatibility among EVA, SBS and TPEE, and capability of solving the problem of nonuniform mixing of EVA/TPEE, so that cracks in the material are passivated, thereby realizing uniform pores and improving foaming efficiency. The invention passes through supercritical N 2The foaming technology has the advantages of wide foaming temperature range, uniform pore distribution, controllable pore size, light weight, high strength, high mechanical property and service performance, high tensile strength, high elongation at break, good tear resistance, low density, extremely low compression deformation and excellent wear resistance. The foaming process is environment-friendly, and the produced product has no foaming agent and no odor of a crosslinking agent, can obtain the same mechanical property as a chemical foaming material, and has a far-reaching application prospect.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer". "interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to polymers prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to polymers prepared from three different monomers). It also includes polymers made by polymerizing four or more monomers. "blend" means a polymer formed by two or more polymers being mixed together by physical or chemical means.
In order to solve the technical problems, the invention provides a material for EVA/TPEE supercritical foaming composite shoes, which is prepared from the following raw materials in parts by weight: 30-40 parts of ethylene-vinyl acetate copolymer, 30-40 parts of thermoplastic polyester elastomer, 10-20 parts of styrene-butadiene block copolymer, 5-8 parts of polyether grafted polyethylene maleic anhydride copolymer, 1-3 parts of peroxide and 1.2-1.6 parts of nucleating agent.
In one embodiment, the EVA/TPEE supercritical foaming composite shoe material is prepared from at least the following raw materials: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 6 parts of polyether grafted polyethylene maleic anhydride copolymer, 2 parts of peroxide and 1.4 parts of nucleating agent.
Ethylene-vinyl acetate copolymer
In the invention, the ethylene-vinyl acetate copolymer is a general high molecular polymer, EVA for short, and the molecular formula is (C)2H4)x.(C4H6O2)yIt is flammable and has no irritation to combustion smell. The shoe material is the most main application field of the EVA resin in China. Because the EVA resin blended foaming product has the performances of softness, good elasticity, chemical corrosion resistance and the like, the EVA resin blended foaming product is widely applied to soles and interior materials of medium and high-grade travel shoes, climbing shoes, slippers and sandals.
In one embodiment, the ethylene-vinyl acetate copolymer has a melt mass flow rate (190 ℃, 2.16kg) of 2.5 to 4g/10 min; preferably, the ethylene-vinyl acetate copolymer has a melt mass flow rate (190 ℃, 2.16kg) of 4g/10 min.
The melt mass flow rate is the melt mass flow rate at 190 ℃ under test method ASTM D1238, 2.16kg, expressed as melt mass flow rate (190 ℃, 2.16 kg).
In one embodiment, the ethylene-vinyl acetate copolymer has a vinyl acetate (VO) content of 18 to 26 wt%; preferably, the ethylene-vinyl acetate copolymer has a vinyl acetate (VO) content of 26 wt%.
In view of the preferred technical effect of the present invention, the ethylene-vinyl acetate copolymer was purchased from Taiko industries, Inc. of Taiko under the brand number TAISOX7470M, the melt mass flow rate (190 ℃, 2.16kg) was 4g/10min, and the vinyl acetate (VO) content was 26 wt%.
Thermoplastic polyester elastomer
In the invention, the thermoplastic polyester elastomer (TPEE), also called polyester rubber, is a linear block copolymer containing PBT (polybutylene terephthalate) polyester hard segment and aliphatic polyester or polyether soft segment.
In one embodiment, the thermoplastic polyester elastomer has a shore D hardness of 40 to 63; preferably, the shore D hardness of the thermoplastic polyester elastomer is 55.
The shore hardness D test method of the thermoplastic polyester elastomer is ISO 868.
In one embodiment, the thermoplastic polyester elastomer has a density of 1.15 to 1.23g/cm3(ii) a Preferably, the density of the thermoplastic polyester elastomer is 1.2g/cm3。
In view of the preferred technical effect of the present invention, the thermoplastic polyester elastomer is given a brand number of
TPEE 1155-201LL, Shore D is 55, density is 1.2g/cm3Purchased from the taiwan vinpock group.
Styrene-butadiene block copolymer
In the invention, the styrene-butadiene block copolymer, abbreviated as SBS, is mainly used for asphalt modification and shoe making, and can also be used as pipes, belts, plates, automobile parts, medical instruments, sports goods and adhesives. Can be used together with resin and rubber for modification, and can be used as filler for adjusting viscosity, hardness, softness, cohesiveness and flexibility.
In one embodiment, the styrene-butadiene block copolymer is a linear styrene-butadiene block copolymer.
In one embodiment, the styrene-butadiene block copolymer has a bound styrene content of 28.5 to 31.5 weight percent.
In one embodiment, the styrene-butadiene block copolymer has a viscosity of 9 to 19cSt (toluene, 25 ℃).
The viscosity of the styrene-butadiene block copolymer was measured by ASTM D445.
In view of the preferred technical effect of the present invention, the styrene-butadiene block copolymer is available under the trade name SIBURSYNYNTHETIC Rubber SBS L30-01A, with a combined styrene content of 28.5-31.5 wt% and a viscosity of 9-19cSt (toluene, 25 ℃) and is purchased from Russian West Boolean, Inc.
Polyether grafted polyethylene maleic anhydride copolymer
In one embodiment, the polyether grafted polyethylene maleic anhydride copolymer is a polyethylene glycol monomethyl ether grafted polyethylene maleic anhydride copolymer.
In one embodiment, the method for preparing the polyethylene glycol monomethyl ether grafted polyethylene maleic anhydride copolymer comprises the following steps:
(1) adding a polyethylene glycol monomethyl ether and polyethylene maleic anhydride copolymer into a three-neck flask with a stirring rod, adding p-toluenesulfonic acid by using xylene as a solvent, heating, carrying out reflux reaction, and removing water by using a water separator;
(2) cooling after the reaction is finished, adding methanol for precipitation, performing suction filtration, washing and drying;
The mass ratio of the polyethylene glycol monomethyl ether to the polyethylene maleic anhydride copolymer is 4: 1; the p-toluenesulfonic acid accounts for 4 wt% of the total mass of the polyethylene glycol monomethyl ether and polyethylene maleic anhydride copolymer; the temperature of the reflux reaction is 160 ℃, and the reaction time is 8 hours;
the polyethylene glycol monomethyl ether is purchased from Beijing Bailingwei chemical Co., Ltd; the polyethylene maleic anhydride copolymer is of the grade
M603, purchased from DuPont, USA.
Peroxides and their use in the preparation of pharmaceutical preparations
In one embodiment, the peroxide is an organic peroxide.
In one embodiment, the organic peroxide is dicumyl peroxide and/or di-t-butylperoxyisopropyl benzene; preferably, the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9).
Nucleating agent
In one embodiment, the nucleating agent is selected from one or more of nano zinc oxide, nano montmorillonite, nano titanium dioxide, nano calcium carbonate and nano white carbon black; preferably, the nucleating agent is nano zinc oxide.
In one embodiment, the nano zinc oxide has a particle size of 10 to 30 nm; preferably, the particle size of the nano zinc oxide is 25nm, and the nano zinc oxide is purchased from Ji chemical technology Co., Qing Ji, Hebei.
In one embodiment, the raw material for preparing the EVA/TPEE supercritical foaming composite shoe material further comprises 1-3 parts by weight of zinc stearate.
In a preferred embodiment, the raw material for preparing the EVA/TPEE supercritical foaming composite shoe material also comprises 2 parts by weight of zinc stearate.
Zinc stearate
In the invention, the molecular formula of the zinc stearate is [ CH ]3(CH2)16COO]2Zn, CAS No. 557-05-1, is white powder, is insoluble in water, is mainly used as a lubricant and a release agent of styrene resin, phenolic resin and amino resin, and also has the functions of a vulcanization activator and a softening agent in rubber; zinc stearateCan be used as heat stabilizer, lubricant, lubricating grease, accelerator, thickener, etc.
The invention provides a preparation method of an EVA/TPEE supercritical foaming composite shoe material, which at least comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, thermoplastic polyester elastomer, styrene-butadiene block copolymer, nucleating agent, polyether grafted polyethylene maleic anhydride copolymer and zinc stearate, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) And cutting a size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out a pressure relief test piece after gas saturation, and cutting the sample to obtain the EVA/TPEE supercritical foaming composite shoe material.
In one embodiment, the gas is supercritical N2。
In one embodiment, the pressure of the foaming kettle is 12-15 MPa; preferably, the pressure of the foaming kettle is 14 MPa.
In one embodiment, the temperature of the foaming kettle is 135-145 ℃; preferably, the temperature of the foaming kettle is 140 ℃.
In one embodiment, the time for gas saturation is 4-6 h; preferably, the time for the gas saturation is 5 h.
In one embodiment, the time for pressure relief is 10-20 s; preferably, the pressure relief time is 15 s.
Thermoplastic polyester elastomer (TPEE) is a linear block copolymer containing polyester hard segments and aliphatic polyester or polyether soft segments, has excellent elasticity of rubber and easy processability of thermoplastic plastics, and has adjustable hardness. However, TPEE is not high in melt strength, and tends to cause large pores, open pores, or uneven pore diameters during foaming. The inventor unexpectedly found in the research process that the material hole of the foaming composite shoe is prepared by supercritical foaming of ethylene-vinyl acetate copolymer with melt mass flow rate (190 ℃, 2.16kg) of 2.5-4g/10min and VA content of 18-26 wt% and linear styrene-butadiene copolymer SIBUR Synthetic Rubber SBS L30-01A The reason that the ethylene-vinyl acetate copolymer with melt mass flow rate (190 ℃, 2.16kg) of 2.5-4g/10min and VA content of 18-26 wt% and the linear styrene-butadiene block copolymer of SIBAR Synthetic Rubber SBS L30-01A interact with TPEE is probably guessed by the inventor, so that the melt strength of the thermoplastic polyester elastomer can be rapidly and effectively improved to meet the requirement of foaming application, and under the conditions of 12-15MPa and 140 ℃, the polymer/gas homogeneous polymer is easily formed, and the stability of a foamed core is improved by rapidly relieving pressure for 15s, so that the pore diameter distribution of the material for the supercritical foaming composite shoes is uniform, and no open pores or combined pores exist. Furthermore, the inventors have surprisingly found that when a Shore D hardness of 55-63 and a density of 1.2g/cm are used3The thermoplastic polyester elastomer (TPEE) has the advantages that the rebound rate of the material for the supercritical foaming composite shoes is obviously improved, the quality wear rate is obviously reduced, and the reasons guessed by the inventor are probably due to the fact that the Shore D hardness is 55-63 and the density is 1.2g/cm3The rigidity, polarity and crystallinity of the hard segment of the thermoplastic polyester elastomer (TPEE) ensure that the TPEE has outstanding flexibility and fatigue resistance, and the low glass transition temperature and the saturability of the soft segment polyether ensure that the TPEE has excellent low temperature resistance and aging resistance, thereby reducing the mass wear rate of the material for the supercritical foaming composite shoes; the polyethylene glycol monomethyl ether is a strong-polarity hydrophilic branched chain, so that the compatibility among EVA, SBS and TPEE is improved, the problem of uneven EVA mixing can be solved, cracks in the material are passivated, and thus, the foam holes are uniform, small and compact, and the foaming efficiency is improved; and di-tert-butylperoxyisopropyl benzene with 
TPEE 1155-201LL mutually acts, and meanwhile, the rebound rate of the material for the supercritical foaming composite shoes is improved.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Embodiment 1 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 30 parts of ethylene-vinyl acetate copolymer, 30 parts of thermoplastic polyester elastomer, 10 parts of styrene-butadiene block copolymer, 5 parts of polyether grafted polyethylene maleic anhydride copolymer, 1 part of peroxide, 1.2 parts of nucleating agent and 1 part of zinc stearate;
the ethylene-vinyl acetate copolymer was purchased from Taistox 7470M, the melt mass flow rate (190 ℃, 2.16kg) was 4g/10min, the vinyl acetate (VO) content was 26 wt%, and the copolymer was obtained from Tai plastics industries, Inc. of Taiwan;
The thermoplastic polyester elastomer is of the grade
TPEE 1155-201LL, Shore D is 55, density is 1.2g/cm3Purchased from the taiwan changchun group;
the styrene-butadiene block copolymer is a linear styrene-butadiene block copolymer, and is sold as SIBURSYNYthenic Rubber SBS L30-01A, and is purchased from Russian West Boolean, Inc.;
the polyether grafted polyethylene maleic anhydride copolymer is polyethylene glycol monomethyl ether grafted polyethylene maleic anhydride copolymer; the preparation method of the polyethylene glycol monomethyl ether grafted polyethylene maleic anhydride copolymer comprises the following steps:
(1) adding a polyethylene glycol monomethyl ether and polyethylene maleic anhydride copolymer into a three-neck flask with a stirring rod, adding p-toluenesulfonic acid by using xylene as a solvent, heating, carrying out reflux reaction, and removing water by using a water separator;
(2) cooling after the reaction is finished, adding methanol for precipitation, performing suction filtration, washing and drying;
the mass ratio of the polyethylene glycol monomethyl ether to the polyethylene maleic anhydride copolymer is 4: 1; the p-toluenesulfonic acid accounts for 4 wt% of the total mass of the polyethylene glycol monomethyl ether and polyethylene maleic anhydride copolymer; the temperature of the reflux reaction is 160 ℃, and the reaction time is 8 hours;
The polyethylene glycol monomethyl ether is purchased from Beijing Bailingwei chemical Co., Ltd; the polyethylene maleic anhydride copolymer is of the grade
M603, purchased from DuPont, USA;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is nano zinc oxide; the particle size of the nano zinc oxide is 25nm, and the nano zinc oxide is purchased from Beijing of Hebei, Ji chemical technology Co., Ltd;
the CAS number of the zinc stearate is 557-05-1.
The preparation method of the EVA/TPEE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, thermoplastic polyester elastomer, styrene-butadiene block copolymer, nucleating agent, polyether grafted polyethylene maleic anhydride copolymer and zinc stearate, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) cutting a size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out a pressure relief test piece after gas saturation, and cutting the sample to obtain the EVA/TPEE supercritical foaming composite shoe material;
the gas is supercritical N2(ii) a The pressure of the foaming kettle is 12 MPa; the temperature of the foaming kettle is 135 ℃; the gas saturation time is 4 h; the pressure relief time is 10 s.
Example 2
Embodiment 2 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 40 parts of ethylene-vinyl acetate copolymer, 40 parts of thermoplastic polyester elastomer, 20 parts of styrene-butadiene block copolymer, 8 parts of polyether grafted polyethylene maleic anhydride copolymer, 3 parts of peroxide, 1.6 parts of nucleating agent and 3 parts of zinc stearate;
the ethylene-vinyl acetate copolymer was the same as in example 1;
the thermoplastic polyester elastomer is the same as that in example 1;
the styrene-butadiene block copolymer was the same as in example 1;
the polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the CAS number of the zinc stearate is 557-05-1.
The preparation method of the EVA/TPEE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, thermoplastic polyester elastomer, styrene-butadiene block copolymer, nucleating agent, polyether grafted polyethylene maleic anhydride copolymer and zinc stearate, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) Cutting a size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out a pressure relief test piece after gas saturation, and cutting the sample to obtain the EVA/TPEE supercritical foaming composite shoe material;
the gas is supercritical N2(ii) a The pressure of the foaming kettle is 15 MPa; the temperature of the foaming kettle is 145 ℃; the gas saturation time is 6 h; the pressure relief time is 20 s.
Example 3
Embodiment 3 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 6 parts of polyether grafted polyethylene maleic anhydride copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent and 2 parts of zinc stearate;
the ethylene-vinyl acetate copolymer was the same as in example 1;
the thermoplastic polyester elastomer is the same as that in example 1;
the styrene-butadiene block copolymer was the same as in example 1;
the polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
The CAS number of the zinc stearate is 557-05-1.
The preparation method of the EVA/TPEE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, thermoplastic polyester elastomer, styrene-butadiene block copolymer, nucleating agent, polyether grafted polyethylene maleic anhydride copolymer and zinc stearate, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) cutting a size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out a pressure relief test piece after gas saturation, and cutting the sample to obtain the EVA/TPEE supercritical foaming composite shoe material;
the gas is supercritical N2(ii) a The pressure of the foaming kettle is 14 MPa; the temperature of the foaming kettle is 140 ℃; the gas saturation time is 5 h; the pressure relief time is 15 s.
Example 4
Embodiment 4 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 6 parts of polyether grafted polyethylene maleic anhydride copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent and 2 parts of zinc stearate;
The ethylene-vinyl acetate copolymer was purchased from Tai plastic industries, Inc. Tai Wan under the brand of TAISOX 7350M, the melt mass flow rate (190 ℃, 2.16kg) was 2.5g/10min, and the vinyl acetate (VO) content was 18 wt%;
the thermoplastic polyester elastomer is of the grade
TPEE 1140LH with Shore hardness D of 40 and density of 1.15g/cm3Purchased from the taiwan changchun group;
the styrene-butadiene block copolymer was the same as in example 1;
the polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the CAS number of the zinc stearate is 557-05-1.
The preparation steps of the EVA/TPEE supercritical foaming composite shoe material are the same as the example 3.
Example 5
Embodiment 5 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 6 parts of polyether grafted polyethylene maleic anhydride copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent and 2 parts of zinc stearate;
The ethylene-vinyl acetate copolymer was the same as in example 1;
the thermoplastic polyester elastomer is of the grade
TPEE 1163-201LL, Shore D of 63 and density of 1.23g/cm3Purchased from the taiwan changchun group;
the styrene-butadiene block copolymer was the same as in example 1;
the polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the CAS number of the zinc stearate is 557-05-1.
The preparation steps of the EVA/TPEE supercritical foaming composite shoe material are the same as the example 3.
Example 6
Embodiment 6 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 6 parts of polyether grafted polyethylene maleic anhydride copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent and 2 parts of zinc stearate;
the ethylene-vinyl acetate copolymer was the same as in example 1;
the thermoplastic polyester elastomer is of the grade
TPEE 1172LL, Shore D of 72 and density of 1.28g/cm 3Purchased from the taiwan changchun group;
the styrene-butadiene block copolymer was the same as in example 1;
the polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the CAS number of the zinc stearate is 557-05-1.
The preparation steps of the EVA/TPEE supercritical foaming composite shoe material are the same as the example 3.
Example 7
Embodiment 7 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 6 parts of polyether grafted polyethylene maleic anhydride copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent and 2 parts of zinc stearate;
the ethylene-vinyl acetate copolymer was purchased from Tai plastic industries, Inc. of Taiwan, with a trade designation of TAISOX 7870H, a melt mass flow rate (190 ℃, 2.16kg) of 15g/10min, and a vinyl acetate (VO) content of 28 wt%;
the thermoplastic polyester elastomer is the same as that in example 1;
the styrene-butadiene block copolymer was the same as in example 1;
The polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the CAS number of the zinc stearate is 557-05-1.
The preparation steps of the EVA/TPEE supercritical foaming composite shoe material are the same as the example 3.
Example 8
Embodiment 8 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 6 parts of polyether grafted polyethylene maleic anhydride copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent and 2 parts of zinc stearate;
the ethylene-vinyl acetate copolymer was the same as in example 1;
the thermoplastic polyester elastomer is the same as that in example 1;
the styrene-butadiene block copolymer is a branched styrene-butadiene block copolymer, and is available under the trade name of SIBURSYNYthenic Rubber SBS L30-00A, and is purchased from Russian West Boolean, Inc.;
the polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
The peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the CAS number of the zinc stearate is 557-05-1.
The preparation steps of the EVA/TPEE supercritical foaming composite shoe material are the same as the example 3.
Example 9
Embodiment 9 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 0 part of polyether grafted polyethylene maleic anhydride copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent and 2 parts of zinc stearate;
the ethylene-vinyl acetate copolymer was the same as in example 1;
the thermoplastic polyester elastomer is the same as that in example 1;
the styrene-butadiene block copolymer was the same as in example 1;
the polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the CAS number of the zinc stearate is 557-05-1.
The preparation steps of the EVA/TPEE supercritical foaming composite shoe material are the same as the example 3.
Example 10
Embodiment 10 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 6 parts of polyether grafted polyethylene maleic anhydride copolymer, 0 part of peroxide, 1.4 parts of nucleating agent and 2 parts of zinc stearate;
the ethylene-vinyl acetate copolymer was the same as in example 1;
the thermoplastic polyester elastomer is the same as that in example 1;
the styrene-butadiene block copolymer was the same as in example 1;
the polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the CAS number of the zinc stearate is 557-05-1.
The preparation steps of the EVA/TPEE supercritical foaming composite shoe material are the same as the example 3.
Example 11
Embodiment 11 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 6 parts of polyether grafted polyethylene maleic anhydride copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent and 2 parts of zinc stearate;
The ethylene-vinyl acetate copolymer was the same as in example 1;
the thermoplastic polyester elastomer is the same as that in example 1;
the styrene-butadiene block copolymer was the same as in example 1;
the polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the CAS number of the zinc stearate is 557-05-1.
The preparation method of the EVA/TPEE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, thermoplastic polyester elastomer, styrene-butadiene block copolymer, nucleating agent, polyether grafted polyethylene maleic anhydride copolymer and zinc stearate, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) cutting a size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out a pressure relief test piece after gas saturation, and cutting the sample to obtain the EVA/TPEE supercritical foaming composite shoe material;
the gas is supercritical N2(ii) a The pressure of the foaming kettle is 18 MPa; the temperature of the foaming kettle is 110 ℃; the gas saturation time is 5 h; the pressure relief time is 15 s.
Example 12
Embodiment 12 provides an EVA/TPEE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 35 parts of thermoplastic polyester elastomer, 15 parts of styrene-butadiene block copolymer, 6 parts of polyether grafted polyethylene maleic anhydride copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent and 2 parts of zinc stearate;
the ethylene-vinyl acetate copolymer was the same as in example 1;
the thermoplastic polyester elastomer is the same as that in example 1;
the styrene-butadiene block copolymer was the same as in example 1;
the polyether grafted polyethylene maleic anhydride copolymer was the same as in example 1;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the CAS number of the zinc stearate is 557-05-1.
The preparation method of the EVA/TPEE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, thermoplastic polyester elastomer, styrene-butadiene block copolymer, nucleating agent, polyether grafted polyethylene maleic anhydride copolymer and zinc stearate, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) Cutting a size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out a pressure relief test piece after gas saturation, and cutting the sample to obtain the EVA/TPEE supercritical foaming composite shoe material;
the gas is supercritical N2(ii) a The pressure of the foaming kettle is 14 MPa; the temperature of the foaming kettle is 140 ℃; the gas saturation time is 3 h; the pressure relief time is 40 s.
Performance testing
1. Average cell size: the average cell diameters of the EVA/TPEE supercritical foamed composite shoe materials described in examples 1-12 were tested by referring to the test method for average cell size of rigid foam described in GB/T12811-1991, wherein the average cell diameter of less than 10 microns is designated A, the average cell diameter of 10-30 microns is designated B, the average cell diameter of 30-50 microns is designated C, and the average cell diameter of more than one micron is designated D, and the test results are shown in Table 1.
2. Appearance: the appearance of the EVA/TPEE supercritical foaming composite shoe material of examples 1-12 was visually observed through a magnifier to see if popping occurred, wherein no popping was recorded as A, a small amount of popping was recorded as B, a large amount of popping was recorded as C, and the test results are shown in Table 1.
3. The mass wear rate is as follows: the EVA/TPEE supercritical foaming composite shoe material obtained in the embodiment 1-12 is ground with phosphor bronze in a way of facing, the test loading force is 200N, the rotating speed is 180rpm, the running time is 2h, the three parallel tests are carried out, the average value is taken, the mass wear rate is recorded, and the test result is shown in the table 1.
Table 1 examples 1-12 performance test results
4. Hardness: the hardness of the composite shoe material described in example 3 was tested with reference to GB/T2411, and the test results are shown in Table 2.
5. Tensile strength: the tensile strength of the composite footwear material described in example 3 was tested with reference to GB/T528 and the results are shown in Table 2.
6. Peel strength: the peel strength of the composite shoe material described in example 3 was tested with reference to GB/T3903, and the test results are shown in Table 2.
7. Tear strength: the tear strength of the composite shoe material described in example 3 was tested with reference to GB/T529 and the results are shown in Table 2.
8. Elongation at break: the elongation at break of the composite footwear material described in example 3 was tested with reference to GB/T528 and the results are shown in Table 2.
9. The rebound rate is as follows: the rebound rate of the composite shoe material described in example 3 was measured by a drop weight test, and the results are shown in table 2.
10. Compression distortion: the compression distortion of the composite shoe material described in example 3 was tested with reference to GB/T7759 and the test results are shown in Table 2.
11. Specific gravity: the specific gravity of the composite shoe material described in example 3 was tested with reference to GB/T1033, and the test results are shown in Table 2.
Table 2 example 3 test results
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The EVA/TPEE supercritical foaming composite shoe material is characterized by comprising the following raw materials in parts by weight: 30-40 parts of ethylene-vinyl acetate copolymer, 30-40 parts of thermoplastic polyester elastomer, 10-20 parts of styrene-butadiene block copolymer, 5-8 parts of polyether grafted polyethylene maleic anhydride copolymer, 1-3 parts of peroxide and 1.2-1.6 parts of nucleating agent.
2. The EVA/TPEE supercritical foamed composite footwear material of claim 1, wherein the melt mass flow rate of the ethylene-vinyl acetate copolymer is 2.5-4g/10 min.
3. The EVA/TPEE supercritical foamed composite footwear material of claim 1, wherein the Shore D hardness of the thermoplastic polyester elastomer is 40-63.
4. The EVA/TPEE supercritical foamed composite footwear material of claim 3, wherein the thermoplastic polyester elastomer has a density of 1.15 to 1.23g/cm3。
5. The EVA/TPEE supercritical foamed composite footwear material of claim 1, wherein the styrene-butadiene block copolymer is a linear styrene-butadiene block copolymer.
6. The EVA/TPEE supercritical foamed composite footwear material of claim 1, wherein the peroxide is an organic peroxide.
7. The EVA/TPEE supercritical foaming composite shoe material as in any one of the claims 1 to 6, wherein the nucleating agent is selected from one or more of nano zinc oxide, nano montmorillonite, nano titanium dioxide, nano calcium carbonate and nano white carbon black.
8. The EVA/TPEE supercritical foamed composite shoe material according to any one of claims 1 to 6, wherein the raw material for preparing the EVA/TPEE supercritical foamed composite shoe material further comprises 1 to 3 parts by weight of zinc stearate.
9. The preparation method of the EVA/TPEE supercritical foaming composite shoe material according to claim 8, which is characterized by at least comprising the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, thermoplastic polyester elastomer, styrene-butadiene block copolymer, nucleating agent, polyether grafted polyethylene maleic anhydride copolymer and zinc stearate, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) and cutting a size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out a pressure relief test piece after gas saturation, and cutting the sample to obtain the EVA/TPEE supercritical foaming composite shoe material.
10. The method for preparing the EVA/TPEE supercritical foaming composite shoe material according to claim 9, characterized in that the gas is supercritical N 2(ii) a The pressure of the foaming kettle is 12-15 MPa; the temperature of the foaming kettle is 135-145 ℃; the gas saturation time is 4-6 h; the pressure relief time is 10-20 s.
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