CN111793268A - EVA/POE supercritical foaming composite shoe material and preparation method thereof - Google Patents
EVA/POE supercritical foaming composite shoe material and preparation method thereof Download PDFInfo
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- 238000005187 foaming Methods 0.000 title claims abstract description 135
- 239000000463 material Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 116
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 116
- 229920001577 copolymer Polymers 0.000 claims abstract description 49
- 239000002667 nucleating agent Substances 0.000 claims abstract description 43
- 150000002978 peroxides Chemical class 0.000 claims abstract description 43
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 50
- 238000012360 testing method Methods 0.000 claims description 49
- 239000003607 modifier Substances 0.000 claims description 40
- 235000021355 Stearic acid Nutrition 0.000 claims description 39
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 39
- 239000008117 stearic acid Substances 0.000 claims description 39
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 28
- 238000005520 cutting process Methods 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- -1 polyethylene maleic anhydride copolymer Polymers 0.000 claims description 18
- 238000005469 granulation Methods 0.000 claims description 13
- 230000003179 granulation Effects 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 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
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-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
- 229940105296 zinc peroxide Drugs 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 12
- 238000007906 compression Methods 0.000 abstract description 6
- 230000006835 compression Effects 0.000 abstract description 6
- 239000004088 foaming agent Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 238000013012 foaming technology Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 20
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 15
- 239000002202 Polyethylene glycol Substances 0.000 description 15
- 229920001223 polyethylene glycol Polymers 0.000 description 15
- 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 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000006260 foam Substances 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
- 229920003051 synthetic elastomer Polymers 0.000 description 5
- 239000005061 synthetic rubber Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000010261 cell growth Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000005060 rubber Substances 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
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 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
- 239000010426 asphalt Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 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
- A43B1/0009—Footwear characterised by the material made at least partially of alveolar or honeycomb material
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
-
- 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
-
- 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
- C08J2203/04—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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Emergency Medicine (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 belongs to the technical field of footwear products, and particularly relates to an EVA/POE supercritical foaming composite shoe material and a preparation method thereof.The EVA/POE supercritical foaming composite shoe material comprises the following raw materials in parts by weight: 30-40 parts of ethylene-vinyl acetate copolymer, 20-30 parts of ethylene-octene copolymer, 10-20 parts of styrene-butadiene block copolymer, 1-3 parts of peroxide and 1.2-1.6 parts of nucleating agent. The invention passes through supercritical N2The 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, the produced product has no smell of foaming agent and cross-linking agent, and can obtain the same mechanical property as the chemical foaming material, thus having a far-reaching application prospect.
Description
Technical Field
The invention belongs to the technical field of footwear products, and particularly relates to an EVA/POE supercritical foaming composite shoe material and a preparation method thereof.
Background
The cell diameter of the common foam is generally more than 50 microns, and the cell density is less than 106/cm3However, the conventional foam plastics have relatively large pore size cells inside, so that the material is often used as a source of foam body cracks when being subjected to external force, thereby reducing the mechanical properties of the material and influencing the application field of the material.
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, because the chemical foaming EVA contains a chemical foaming agent and a chemical crosslinking agent in a base material, the chemical foaming EVA is easy to have the problems that the foaming agent is remained and is not friendly to the environment, and has slight smell, the foaming is not uniform due to the nonuniform mixing of the foaming agent, the quality is influenced, and the like, and a better foaming method is searched for replacing the chemical foaming EVA in the industry.
Disclosure of Invention
In order to solve the technical problems, the invention provides an EVA/POE supercritical foaming composite shoe material in a first aspect, and the preparation raw materials of the supercritical foaming composite shoe material at least comprise the following components in parts by weight: 30-40 parts of ethylene-vinyl acetate copolymer, 20-30 parts of ethylene-octene copolymer, 10-20 parts of styrene-butadiene block copolymer, 1-3 parts of peroxide and 1.2-1.6 parts of nucleating agent.
As a preferable technical scheme, the content of the vinyl acetate in the ethylene-vinyl acetate copolymer is 26-28 wt%.
As a preferred technical proposal, the density of the ethylene-octene copolymer is 0.862 to 0.885g/cm3。
As a preferred technical scheme, the peroxide is selected from one or more of zinc peroxide, dicumyl peroxide and di-tert-butylperoxyisopropyl benzene.
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 preparation raw materials of the supercritical foaming composite shoe material further comprise the following components in parts by weight: 5-8 parts of modifier and 1-3 parts of stearic acid.
As a preferred technical scheme, the modifier is polyether grafted polyethylene maleic anhydride copolymer.
The second aspect of the invention provides a preparation method of the EVA/POE supercritical foaming composite shoe material, which at least comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) and cutting the size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out the pressure relief test piece after gas saturation, and cutting the sample to obtain the supercritical foaming composite shoe material.
As a preferable technical scheme, the pressure of the foaming kettle is 16-20 MPa; the temperature of the foaming kettle is 105-115 ℃.
As a preferred technical scheme, the gas is supercritical N2(ii) a The gas saturation time is 2.5-3.5 h; the pressure relief time is 20-40 s.
Has the advantages that: the EVA/POE supercritical foaming composite shoe material provided by the invention has the pore diameter generally less than 10 microns and the pore density more than 108 pores/cm3Due to the smaller pore diameter and the uniform distribution in the polymer materialSo that the cracks in the material are passivated, and the performance of the foaming material can be improved. The invention passes through supercritical N2The 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, the produced product has no smell of foaming agent and cross-linking agent, and can obtain the same mechanical property as the chemical foaming material, thus having 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 an EVA/POE supercritical foaming composite shoe material in a first aspect, and the preparation raw materials of the supercritical foaming composite shoe material at least comprise the following components in parts by weight: 30-40 parts of ethylene-vinyl acetate copolymer, 20-30 parts of ethylene-octene copolymer, 10-20 parts of styrene-butadiene block copolymer, 1-3 parts of peroxide and 1.2-1.6 parts of nucleating agent.
In one embodiment, the supercritical foaming composite shoe material is prepared from at least the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 25 parts of ethylene-octene copolymer, 15 parts of styrene-butadiene block 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. In the EVA resin used for the shoe material, the vinyl acetate content is generally 15 to 22 wt%. 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 vinyl acetate content of 26 to 28 wt%.
In a preferred embodiment, the ethylene-vinyl acetate copolymer is a blend of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 26 wt% and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 28 wt%.
In one embodiment, the ethylene-vinyl acetate copolymer having a vinyl acetate content of 26 wt% and the ethylene-vinyl acetate copolymer having a vinyl acetate content of 28 wt% are present in a mass ratio of 1: (1.2-1.6); preferably, the mass ratio of the ethylene-vinyl acetate copolymer with the vinyl acetate content of 26 wt% to the ethylene-vinyl acetate copolymer with the vinyl acetate content of 28 wt% is 1: 1.5.
in one embodiment, the ethylene-vinyl acetate copolymer having a vinyl acetate content of 26 wt% is available under the designation EVA 7470K from Taiwan industries, Inc.
In one embodiment, the ethylene-vinyl acetate copolymer having a vinyl acetate content of 28 wt% is sold under the designation LG EVA28400 and/or Yangzibasfu-6110M; preferably, the ethylene-vinyl acetate copolymer having a vinyl acetate content of 28 wt% is available under the designation LG EVA28400, available from plastification import and export ltd, reprocessed, su.
Ethylene-octene copolymer
In the present invention, the ethylene-octene copolymer refers to a polymer of 1-octene and ethylene.
In one embodiment, the ethylene-octene copolymer has a density of 0.862 to 0.885g/cm3(ii) a Preferably, the ethylene-octene copolymer has a density of 0.87g/cm3。
In one embodiment, the ethylene-octene copolymer is of a grade selected from one or more of TAFMER H-10308, TAFMERDF940, TAFMER DF 740; preferably, the ethylene-octene copolymer is available under the trademark TAFMER H-10308, available from Mitsui, Japan.
Styrene-butadiene block copolymer
In the invention, the styrene-butadiene block copolymer, SBS for short, is mainly used for asphalt modification and shoemaking, and can also be used as a pipe; tapes, panels, automotive parts, medical devices, sporting 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 branched polymeric structure.
In one embodiment, the styrene-butadiene block copolymer has a bound styrene content of 28.5 to 31.5 weight percent and a viscosity of 25 to 35cSt (toluene, 25 ℃), under the trade designation SIBAR Synthetic Rubber SBS L30-00A, available from Russian Limited company.
Peroxides and their use in the preparation of pharmaceutical preparations
In one embodiment, the peroxide is selected from one or more of zinc peroxide, dicumyl peroxide, 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 materials for preparing the supercritical foaming composite shoe material further comprise the following components in parts by weight: 5-8 parts of modifier and 1-3 parts of stearic acid.
In a preferred embodiment, the raw materials for preparing the supercritical foaming composite shoe material further comprise the following components in parts by weight: 7 parts of modifier and 2 parts of stearic acid.
Modifying agent
In one embodiment, the modifier is a 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.
The inventor finds that when EVA with the vinyl acetate content of 26-28 wt% is adopted, particularly the mass ratio of LG EVA28400 to EVA 7470K is (1.2-1.6): 1, the composite shoe material has good foaming effect, large elongation at break, good tear resistance and extremely low compression deformation. The reason the inventors guess may be that due to the vinyl acetate content of 26-28 wt%, EVA has good resilience, flexibility, adhesion, transparency, solubility, stress crack resistance and impact performance without reducing the rigidity, abrasion resistance and electrical insulation of EVA. Furthermore, the inventors have surprisingly found that the use of a density of 0.862 to 0.885g/cm3The composite shoe material prepared by the POE, the SBS with the branched polymer structure, the polyethylene glycol monomethyl ether grafted polyethylene maleic anhydride copolymer and the EVA has uniform, small and compact pores, and the foaming process is environment-friendly and odorless. The reason the inventor guesses may be that the compatibility among EVA, POE and SBS is improved because the polyethylene glycol monomethyl ether is a strong polar hydrophilic branched chain, the problem of uneven EVA mixing can be solved, and the composite shoe material has smaller aperture, the aperture is generally less than 10 microns, and the aperture density is more than 108/cm3And the smaller pore diameter is uniformly distributed in the high polymer material, so that cracks in the material are passivated, and the foam holes are uniform, small and compact, and have good foaming effect and high foaming efficiency. Simultaneously, the octene chain segment in POE destroys part of polyethylene crystals to play a role of physical crosslinking, and SIBUR SyntheticThe branched polymer structure of Rubber SBS L30-00A can also raise the wear resistance and tear resistance of the composite shoe material and make the compression deformation extremely low.
Stearic acid
In the present invention, the CAS number of stearic acid is 57-11-4.
The second aspect of the invention provides a preparation method of the EVA/POE supercritical foaming composite shoe material, which at least comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) and cutting the size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out the pressure relief test piece after gas saturation, and cutting the sample to obtain the supercritical foaming composite shoe material.
In one embodiment, the foaming vessel has a pressure of 16 to 20 MPa; preferably, the pressure of the foaming kettle is 18 MPa.
In one embodiment, the temperature of the foaming vessel is 105-; preferably, the temperature of the foaming kettle is 110 ℃.
In one embodiment, the gas is supercritical N2。
In one embodiment, the time for saturation of the gas is 2.5 to 3.5 hours; preferably, the time for the gas saturation is 3 h.
In one embodiment, the time for pressure relief is 20-40 s; preferably, the pressure relief time is 30 s.
The invention passes through supercritical N2The foaming technology has wide foaming temperature range, the foaming process is environment-friendly, the produced product has no smell of foaming agent and cross-linking agent, and the mechanical property which is the same as that of the chemical foaming material can be obtained. The inventor unexpectedly finds that when the pressure of the foaming kettle is 16-20MPa, the temperature of the foaming kettle is 110 ℃, the gas saturation time is 3h, and the pressure relief time is 30s, the foam holes are uniformly distributed, the pore size is controllable, and the reason guessed by the inventor is thatCan be obtained by supercritical N under the conditions of 16-20MPa pressure and 110 deg.C temperature2Can be well dissolved in the polymer through diffusion to form a polymer/gas homogeneous polymer; the polymer/gas homogeneous system reaches a saturated state through rapid pressure relief for 30s, high-energy gas molecules are mutually aggregated to form a stable bubble nucleus, and the bis-tert-butylperoxyisopropyl benzene is in a branched macromolecular structure of SIBAR Synthetic Rubber SBS L30-00A and under the action of TAFMER H-10308 and EVA, so that the cross-linking density in the foaming process is proper, a continuous pore structure cannot be formed or foaming cannot be performed due to gas inclusion, and the phenomenon that the foaming multiplying power is small or foaming cannot be performed due to too high melt strength caused by too high cross-linking density in the foaming process is avoided; the gas saturation time of 3h enables the gas in the system to gradually diffuse into the bubble nucleus, so that the bubble hole is increased; the branched polymer structure of the SIBUR Synthetic Rubber SBS L30-00A improves the melt strength of the polymer, and the polyethylene glycol monomethyl ether is a strong polar hydrophilic branched chain which can reduce the driving force of cell growth, so that the cell growth stops, and finally the structure of the cells is fixed, the cells are distributed uniformly, and the pore size is controllable.
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/POE supercritical foaming composite shoe material, which is prepared from the following raw materials in parts by weight: 30 parts of ethylene-vinyl acetate copolymer, 20 parts of ethylene-octene copolymer, 10 parts of styrene-butadiene block copolymer, 1 part of peroxide, 1.2 parts of nucleating agent, 5 parts of modifier and 1 part of stearic acid;
the ethylene-vinyl acetate copolymer is a compound of an ethylene-vinyl acetate copolymer with the vinyl acetate content of 26 wt% and an ethylene-vinyl acetate copolymer with the vinyl acetate content of 28 wt%; the mass ratio of the ethylene-vinyl acetate copolymer with the vinyl acetate content of 26 wt% to the ethylene-vinyl acetate copolymer with the vinyl acetate content of 28 wt% is 1: 1.2; the ethylene-vinyl acetate copolymer with the vinyl acetate content of 26 wt% is EVA 7470K and is purchased from Taiwan plastic industry Co.Ltd; the ethylene-vinyl acetate copolymer with the vinyl acetate content of 28 wt% is of the brand LG EVA28400 and is purchased from Suzhou Rui plastification import and export Co., Ltd;
the density of the ethylene-octene copolymer is 0.87g/cm3(ii) a The ethylene-octene copolymer is designated by the trademark TAFMER H-10308 and is purchased from Mitsui, Japan;
the styrene-butadiene block copolymer has a bound styrene content of 28.5 to 31.5 wt%, a viscosity of 25 to 35cSt (toluene, 25 ℃), a designation of SIBAR Synthetic Rubber SBS L30-00A, purchased from Russian West Boolean, Inc.;
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 modifier 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 polyethylene glycol monomethyl ether,4 wt% of the total mass of the 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 CAS number of the stearic acid is 57-11-4;
the preparation method of the EVA/POE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, 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 a sample to obtain the supercritical foaming composite shoe material;
the pressure of the foaming kettle is 16 MPa; the temperature of the foaming kettle is 105 ℃; the gas is supercritical N2(ii) a The gas saturation time is 2.5 h; the pressure relief time is 20 s.
Example 2
Embodiment 2 provides an EVA/POE supercritical foaming composite shoe material, which is prepared from the following raw materials in parts by weight: 40 parts of ethylene-vinyl acetate copolymer, 30 parts of ethylene-octene copolymer, 20 parts of styrene-butadiene block copolymer, 3 parts of peroxide, 1.6 parts of nucleating agent, 8 parts of modifier and 3 parts of stearic acid;
the ethylene-vinyl acetate copolymer is the same as example 1 except that the ethylene-vinyl acetate copolymer having a vinyl acetate content of 26 wt% and the ethylene-vinyl acetate copolymer having a vinyl acetate content of 28 wt% are mixed in a mass ratio of 1: 1.6;
the ethylene-octene copolymer was the same as in example 1;
the styrene-butadiene block 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 modifier is the same as in example 1;
the CAS number of the stearic acid is 57-11-4;
the preparation method of the EVA/POE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, 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 a sample to obtain the supercritical foaming composite shoe material;
the pressure of the foaming kettle is 20 MPa; the temperature of the foaming kettle is 115 ℃; the gas is supercritical N2(ii) a The gas saturation time is 3.5 h; the pressure relief time is 40 s.
Example 3
Embodiment 3 provides an EVA/POE supercritical foaming composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 25 parts of ethylene-octene copolymer, 15 parts of styrene-butadiene block copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent, 7 parts of modifier and 2 parts of stearic acid;
the ethylene-vinyl acetate copolymer is the same as example 1 except that the ethylene-vinyl acetate copolymer having a vinyl acetate content of 26 wt% and the ethylene-vinyl acetate copolymer having a vinyl acetate content of 28 wt% are mixed in a mass ratio of 1: 1.4;
the ethylene-octene copolymer was the same as in example 1;
the styrene-butadiene block 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 modifier is the same as in example 1;
the CAS number of the stearic acid is 57-11-4;
the preparation method of the EVA/POE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, 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 a sample to obtain the supercritical foaming composite shoe material;
the pressure of the foaming kettle is 18 MPa; the temperature of the foaming kettle is 110 ℃; the gas is supercritical N2(ii) a The gas saturation time is 3 h; the pressure relief time is 30 s.
Example 4
Embodiment 4 provides an EVA/POE supercritical foaming composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 25 parts of ethylene-octene copolymer, 15 parts of styrene-butadiene block copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent, 7 parts of modifier and 2 parts of stearic acid;
the ethylene-vinyl acetate copolymer is the same as example 1 except that the ethylene-vinyl acetate copolymer having a vinyl acetate content of 26 wt% and the ethylene-vinyl acetate copolymer having a vinyl acetate content of 28 wt% are mixed in a mass ratio of 1: 0;
the ethylene-octene copolymer was the same as in example 1;
the styrene-butadiene block 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 modifier is the same as in example 1;
the CAS number of the stearic acid is 57-11-4;
the preparation method of the EVA/POE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, 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 a sample to obtain the supercritical foaming composite shoe material;
the pressure of the foaming kettle is 18 MPa; the temperature of the foaming kettle is 110 ℃; the gas is supercritical N2(ii) a The gas saturation time is 3 h; the pressure relief time is 30 s.
Example 5
Embodiment 5 provides an EVA/POE supercritical foaming composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 25 parts of ethylene-octene copolymer, 15 parts of styrene-butadiene block copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent, 7 parts of modifier and 2 parts of stearic acid;
the ethylene-vinyl acetate copolymer is the same as example 1 except that the ethylene-vinyl acetate copolymer having a vinyl acetate content of 26 wt% and the ethylene-vinyl acetate copolymer having a vinyl acetate content of 28 wt% are mixed in a mass ratio of 0: 1.4;
the ethylene-octene copolymer was the same as in example 1;
the styrene-butadiene block 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 modifier is the same as in example 1;
the CAS number of the stearic acid is 57-11-4;
the preparation method of the EVA/POE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, 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 a sample to obtain the supercritical foaming composite shoe material;
the pressure of the foaming kettle is 18 MPa; the temperature of the foaming kettle is 110 ℃; the gas is supercritical N2(ii) a The gas saturation time is 3 h; the pressure relief time is 30 s.
Example 6
Embodiment 6 provides an EVA/POE supercritical foaming composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 25 parts of ethylene-octene copolymer, 15 parts of styrene-butadiene block copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent, 7 parts of modifier and 2 parts of stearic acid;
the ethylene-vinyl acetate copolymer was the same as in example 3;
the ethylene-octene copolymer was the same as in example 1;
the styrene-butadiene block 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 modifier is maleic anhydride grafted polyethylene with the trade name of TY1355 which is purchased from big plastic raw material Co., Ltd of Dongguan city;
the CAS number of the stearic acid is 57-11-4;
the preparation method of the EVA/POE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, 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 a sample to obtain the supercritical foaming composite shoe material;
the pressure of the foaming kettle is 18 MPa; the temperature of the foaming kettle is 110 ℃; the gas is supercritical N2(ii) a The gas saturation time is 3 h; the pressure relief time is 30 s.
Example 7
Embodiment 7 provides an EVA/POE supercritical foaming composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 25 parts of ethylene-octene copolymer, 15 parts of styrene-butadiene block copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent, 7 parts of modifier and 2 parts of stearic acid;
the ethylene-vinyl acetate copolymer was the same as in example 3;
the ethylene-octene copolymer was the same as in example 1;
the styrene-butadiene block copolymer has a bound styrene content of 28.5 to 31.5 wt%, a viscosity of 9 to 19cSt (toluene, 25 ℃), a designation of SIBUR Synthetic Rubber SBS L30-01A, purchased from Russian West Boolean, Inc.;
the peroxide is bis-tert-butylperoxyisopropyl benzene (CAS number 2212-81-9);
the nucleating agent is the same as in example 1;
the modifier is the same as in example 1;
the CAS number of the stearic acid is 57-11-4;
the preparation method of the EVA/POE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, 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 a sample to obtain the supercritical foaming composite shoe material;
the pressure of the foaming kettle is 18 MPa; the temperature of the foaming kettle is 110 ℃; the gas is supercritical N2(ii) a The gas saturation time is 3 h; the pressure relief time is 30 s.
Example 8
Embodiment 8 provides an EVA/POE supercritical foaming composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 25 parts of ethylene-octene copolymer, 15 parts of styrene-butadiene block copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent, 7 parts of modifier and 2 parts of stearic acid;
the ethylene-vinyl acetate copolymer was the same as in example 3;
the ethylene-octene copolymer was the same as in example 1;
the styrene-butadiene block 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 modifier is the same as in example 1;
the CAS number of the stearic acid is 57-11-4;
the preparation method of the EVA/POE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, 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 a sample to obtain the supercritical foaming composite shoe material;
the pressure of the foaming kettle is 18 MPa; the temperature of the foaming kettle is 110 ℃; the gas is supercritical CO2(ii) a The gas saturation time is 3 h; the pressure relief time is 30 s.
Example 9
Embodiment 9 provides an EVA/POE supercritical foaming composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 25 parts of ethylene-octene copolymer, 15 parts of styrene-butadiene block copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent, 7 parts of modifier and 2 parts of stearic acid;
the ethylene-vinyl acetate copolymer was the same as in example 3;
the ethylene-octene copolymer was the same as in example 1;
the styrene-butadiene block 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 modifier is the same as in example 1;
the CAS number of the stearic acid is 57-11-4;
the preparation method of the EVA/POE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, 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 a sample to obtain the supercritical foaming composite shoe material;
the pressure of the foaming kettle is 12 MPa; the temperature of the foaming kettle is 150 ℃; the gas is supercritical N2(ii) a The gas saturation time is 3 h; the pressure relief time is 30 s.
Example 10
Embodiment 10 provides an EVA/POE supercritical foamed composite shoe material, which is prepared from the following raw materials in parts by weight: 35 parts of ethylene-vinyl acetate copolymer, 25 parts of ethylene-octene copolymer, 15 parts of styrene-butadiene block copolymer, 2 parts of peroxide, 1.4 parts of nucleating agent, 7 parts of modifier and 2 parts of stearic acid;
the ethylene-vinyl acetate copolymer was the same as in example 3;
the ethylene-octene copolymer was the same as in example 1;
the styrene-butadiene block 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 modifier is the same as in example 1;
the CAS number of the stearic acid is 57-11-4;
the preparation method of the EVA/POE supercritical foaming composite shoe material comprises the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, 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 a sample to obtain the supercritical foaming composite shoe material;
the pressure of the foaming kettle is 18 MPa; the temperature of the foaming kettle is 110 ℃; the gas is supercritical N2(ii) a The gas saturation time is 3 h; the pressure relief time is 120 s.
Performance testing
1. Wear resistance: the dynamic friction coefficients of the composite shoe materials described in examples 1 to 10 were measured under test conditions of a load p of 200N, a relative linear sliding velocity v of 0.604m/s and a friction time t of 120min according to the method for measuring the friction coefficients of GB10006 to 88 plastic films and sheets, and the test results are shown in Table 1.
2. Average cell size: the average cell diameter of the composite shoe material described in examples 1-10 was tested by reference to the average cell size test method of rigid foam described in GB/T12811-1991, and the test results are shown in Table 1.
Table 1 examples 1-10 performance test results
3. 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.
4. 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.
5. 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.
6. 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.
7. 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.
8. 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.
9. 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.
10. 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/POE supercritical foaming composite shoe material is characterized by at least comprising the following raw materials in parts by weight: 30-40 parts of ethylene-vinyl acetate copolymer, 20-30 parts of ethylene-octene copolymer, 10-20 parts of styrene-butadiene block copolymer, 1-3 parts of peroxide and 1.2-1.6 parts of nucleating agent.
2. The supercritical foamed composite footwear material of claim 1, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 26 to 28 wt%.
3. The supercritical foamed composite footwear material of claim 1, wherein the ethylene-octene copolymer has a density of 0.862 to 0.885g/cm3。
4. The supercritical foamed composite footwear material of claim 1, wherein the peroxide is selected from one or more of zinc peroxide, dicumyl peroxide, di-t-butylperoxyisopropyl benzene.
5. The supercritical foamed composite shoe material as set forth in claim 1, wherein the nucleating agent is one or more selected from the group consisting of nano zinc oxide, nano montmorillonite, nano titanium dioxide, nano calcium carbonate and nano white carbon black.
6. The supercritical foamed composite shoe material according to any one of claims 1 to 5, wherein the supercritical foamed composite shoe material is prepared from the following raw materials in parts by weight: 5-8 parts of modifier and 1-3 parts of stearic acid.
7. The supercritical foamed composite footwear material of claim 6, wherein the modifier is a polyether grafted polyethylene maleic anhydride copolymer.
8. A method for preparing the supercritical foaming composite shoe material according to claim 6 or 7, which is characterized by at least comprising the following steps:
(1) firstly, uniformly mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, styrene-butadiene block copolymer, nucleating agent, modifier and stearic acid, and carrying out double-screw mixing granulation; adding peroxide, banburying and granulating, and tabletting by a flat vulcanizing machine;
(2) and cutting the size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out the pressure relief test piece after gas saturation, and cutting the sample to obtain the supercritical foaming composite shoe material.
9. The method for preparing the supercritical foaming composite shoe material according to the claim 8, wherein the pressure of the foaming kettle is 16-20 MPa; the temperature of the foaming kettle is 105-115 ℃.
10. The method for preparing the supercritical foamed composite shoe material according to claim 8 or 9, wherein the gas is supercritical N2(ii) a The gas saturation time is 2.5-3.5 h; the pressure relief time is 20-40 s.
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| CN115340721A (en) * | 2022-09-01 | 2022-11-15 | 东莞市国立飞织制品有限公司 | Shoe material containing bio-based EVA (ethylene vinyl acetate) and preparation method and application thereof |
| CN115340721B (en) * | 2022-09-01 | 2024-07-12 | 东莞市国立飞织制品有限公司 | Shoe material containing bio-based EVA and preparation method and application thereof |
| CN115466453A (en) * | 2022-09-22 | 2022-12-13 | 青岛昶捷科技有限公司 | Supercritical foaming material containing reclaimed materials and preparation method thereof |
| CN115466453B (en) * | 2022-09-22 | 2023-08-22 | 青岛昶捷科技有限公司 | Supercritical foaming material containing reclaimed materials and preparation method thereof |
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