CN115124780A - Antibacterial high-strength EVA (ethylene-vinyl acetate) foaming shoe material containing natural extract - Google Patents
Antibacterial high-strength EVA (ethylene-vinyl acetate) foaming shoe material containing natural extract Download PDFInfo
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- CN115124780A CN115124780A CN202210725566.5A CN202210725566A CN115124780A CN 115124780 A CN115124780 A CN 115124780A CN 202210725566 A CN202210725566 A CN 202210725566A CN 115124780 A CN115124780 A CN 115124780A
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- shoe material
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- 239000000463 material Substances 0.000 title claims abstract description 106
- 239000000284 extract Substances 0.000 title claims abstract description 85
- 238000005187 foaming Methods 0.000 title claims abstract description 68
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 50
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 title abstract description 102
- 239000005038 ethylene vinyl acetate Substances 0.000 title abstract description 102
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title abstract description 102
- 239000000945 filler Substances 0.000 claims abstract description 47
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229920001661 Chitosan Polymers 0.000 claims abstract description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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 abstract description 10
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 235000010216 calcium carbonate Nutrition 0.000 claims abstract description 5
- 235000019359 magnesium stearate Nutrition 0.000 claims abstract description 5
- 235000020230 cinnamon extract Nutrition 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 17
- 229920002401 polyacrylamide Polymers 0.000 claims description 16
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 12
- 239000004156 Azodicarbonamide Substances 0.000 claims description 7
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 7
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 230000003385 bacteriostatic effect Effects 0.000 description 13
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000003801 milling Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229940069445 licorice extract Drugs 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 229910004354 OF 20 W Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/009—Use of pretreated compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- 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
- C08J2203/18—Binary blends of expanding agents
-
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
- C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The application relates to the field of shoe materials, and particularly discloses an antibacterial high-strength EVA (ethylene-vinyl acetate) foamed shoe material containing a natural extract, which is prepared from the following raw materials: EVA, natural extract, foaming agent, cross-linking agent, dicumyl peroxide and filler; the filler is at least two of calcium carbonate, kaolin and magnesium stearate; the natural extract is one or more of chitosan, oat extract and cinnamon extract; pretreating the filler by using a natural extract; the natural extract is modified in advance by the following method: adding the natural extract into a reaction bottle, adding 1-5wt% acetic acid aqueous solution, heating to 65-78 deg.C, stirring to dissolve, introducing nitrogen to remove oxygen, adding ethyl acrylate and potassium persulfate, reacting for 1-2h, adding 1-5wt% sodium hydroxide aqueous solution to neutralize, collecting precipitate, washing with water to neutrality, and drying to obtain modified extract. The application has the effect of improving the antibacterial property of the EVA foaming shoe material.
Description
Technical Field
The application relates to the field of shoe materials, in particular to an antibacterial high-strength EVA foaming shoe material containing a natural extract.
Background
EVA is ethylene vinyl acetate (vinyl acetate) copolymer, it is made by ethylene and vinyl acetate copolymerization, EVA because introduce vinyl acetate monomer in the molecular chain, so EVA has very big improvement in the performance aspect compared with PE, for example EVA has better flexibility, impact resistance, filler compatibility and heat sealing performance, because EVA has these good performances, so it is applied to fields such as foamed shoe material, functional shed membrane, packaging film, hot melt adhesive, wire and cable and toy extensively, wherein foamed shoe material is the most important application field of EVA resin in our country.
However, because the existing EVA foaming shoe material has poor antibacterial performance, the prepared EVA foaming shoe material is easy to breed bacteria to cause odor, and the use of people is influenced. Therefore, there is still room for improvement.
Disclosure of Invention
In order to improve the antibacterial performance of the EVA foaming shoe material, the application provides an antibacterial high-strength EVA foaming shoe material containing a natural extract.
The application provides an antibiotic high strength EVA foaming shoe material that contains natural extract adopts following technical scheme: an antibacterial high-strength EVA foaming shoe material containing natural extracts is prepared from the following raw materials in parts by weight:
110-150 parts of EVA; 14-22 parts of natural extracts; 6-12 parts of a foaming agent; 1-2 parts of a crosslinking agent; 0.5-1 part of dicumyl peroxide; 5-9 parts of a filler;
the filler is at least two of calcium carbonate, kaolin and magnesium stearate;
the natural extract is one or more of chitosan, oat extract and cinnamon extract;
the filler is pretreated by natural extracts;
the natural extract is modified in advance by the following method: adding the natural extract into a reaction bottle, adding 1-5wt% of acetic acid aqueous solution, heating to 65-78 ℃, stirring for dissolving, introducing nitrogen to remove oxygen, adding an ethyl acrylate monomer and a potassium persulfate initiator, reacting for 1-2h, adding 1-5wt% of sodium hydroxide aqueous solution for neutralization, collecting precipitate, washing with water to neutrality, and drying to obtain the modified extract.
By adopting the technical scheme, the EVA is used as the basic raw material of the shoe material, dicumyl peroxide is used as the initiator of the cross-linking agent, chitosan, oat extract and cinnamon extract all have certain antibacterial effect, then the natural extract is modified by adopting the method, and then the filler is pretreated by the modified extract, so that the interface bonding force between the filler and the polymer matrix resin is enhanced, the antibacterial performance of the EVA foaming shoe material is improved, meanwhile, the filler is not easy to agglomerate, and further the pore structure of the foaming material is uniform and fine, so that the phenomenon of local expansion is not easy to occur in the EVA foaming process, the EVA foaming shoe material is not easy to crack, and the mechanical strength of the EVA foaming shoe material is improved.
Preferably, the EVA foaming shoe material further comprises the following raw materials in parts by weight:
2-4 parts of dodecyl dimethyl benzyl ammonium chloride;
11-17 parts of polyacrylamide.
By adopting the technical scheme, the polyacrylamide is added into the EVA foaming shoe material, so that the antibacterial durability of the EVA foaming shoe material is favorably improved. However, in the research and development process of research and development personnel, after polyacrylamide is added, the polyacrylamide and the polyethylacrylate are mutually exclusive, so that the filler subjected to surface treatment by the modified extract is easy to delaminate in a system, the modified filler cannot be well mixed with other raw materials, and the antibacterial performance of the EVA foaming shoe material is reduced. Through a large amount of researches, the fact that dodecyl dimethyl benzyl ammonium chloride in a specific proportion is added to be matched with polyacrylamide, the uniformity of the filler in a system is improved, and the dodecyl dimethyl benzyl ammonium chloride is a cationic surfactant, has dispersing and penetrating effects and is combined with polyacrylamide, so that the filler treated by the modified extract is mixed more uniformly in the system, and the antibacterial performance of the EVA foamed shoe material is improved; the washing fastness of the EVA foaming shoe material is improved, and after washing for many times, the antibacterial performance of the EVA foaming shoe material is not easy to reduce, so that the EVA foaming shoe material can keep the antibacterial performance for a long time, and the comfort of the shoe is kept for a long time.
Preferably, the natural extract is prepared from the following components in a mass ratio of 1: (1.1-1.3) chitosan and oat extract.
By adopting the technical scheme, the chitosan and the oat extract in a specific proportion are matched with each other, so that the antibacterial performance of the EVA foaming shoe material is favorably improved, the washing fastness of the EVA foaming shoe material is further favorably improved, the antibacterial performance of the EVA foaming shoe material after being washed for multiple times is not easy to reduce, and the service life of the EVA foaming shoe material is longer.
Preferably, the chitosan has an average molecular weight of 55-80 w.
By adopting the technical scheme, the chitosan adopts the average molecular weight in a specific range, which is beneficial to further improving the antibacterial performance of the EVA foaming shoe material.
Preferably, the filler is prepared from calcium carbonate and kaolin according to a mass ratio of (1.2-2): 2, mixing the components.
Through adopting above-mentioned technical scheme, adopt specific proportion's calcium carbonate and kaolin to mutually support, be favorable to further improving the homogeneity of expanded material's pore structure for it is difficult for the reunion to pack, and then makes expanded material's wholeness more even, improves the pliability of EVA foaming shoes material with this better, makes people wear the shoes that are made by EVA foaming shoes material and feel softer and comfortable more.
Preferably, the foaming agent is one or more of azodicarbonamide, barium azodicarboxylate, azoaminobenzene and azobisisobutyronitrile.
By adopting the technical scheme, the foaming agent is prepared from the substances, so that the mixing of the filler treated by the modified extract in a system is facilitated, the antibacterial performance of the EVA foaming shoe material is improved, the EVA foaming shoe material is not easy to breed bacteria to cause odor, and the comfort of the EVA foaming shoe material is better.
Preferably, the foaming agent is formed by mixing azodicarbonamide and barium azodicarboxylate in a mass ratio of 1.5: 4.
By adopting the technical scheme, azodicarbonamide and barium azodicarboxylate in a specific proportion are used as foaming agents, so that the antibacterial property and the mechanical property of the EVA foaming shoe material are further improved.
Preferably, the crosslinker is triallyl isocyanurate.
By adopting the technical scheme, the foaming performance of the foaming agent is improved by adopting the triallyl isocyanurate as the cross-linking agent, so that the foam cells are uniform, fine and high in strength, and the foaming material has good mechanical properties.
In summary, the present application includes at least one of the following beneficial technical effects:
1. by adopting the EVA as the basic raw material of the shoe material, then modifying the natural extract by adopting the method, and then pretreating the filler by the modified natural extract, the antibacterial property of the EVA foaming shoe material is favorably improved, the filler is not easy to agglomerate, and further the pore structure of the foaming material is uniform and fine, so that the EVA foaming shoe material is not easy to crack, and the mechanical strength of the EVA foaming shoe material is improved.
2. By adding dodecyl dimethyl benzyl ammonium chloride and polyacrylamide in a specific ratio to be matched with each other, not only is the combination of the modified extract and the filler promoted, but also the washing fastness of the EVA foaming shoe material is improved, so that the EVA foaming shoe material can keep the antibacterial performance for a long time, and the comfort of the shoe is kept for a long time.
3. By adopting the chitosan and the oat extract in a specific ratio to be matched with each other, the antibacterial performance of the EVA foaming shoe material is favorably improved, and the washing fastness of the EVA foaming shoe material is favorably further improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Example 1
The application discloses an antibacterial high-strength EVA (ethylene-vinyl acetate) foaming shoe material containing a natural extract, which is prepared from the following raw materials in parts by weight: EVA; a natural extract; a foaming agent; a crosslinking agent; a filler; dicumyl peroxide;
the filler is formed by mixing calcium carbonate and kaolin; the natural extract is prepared by mixing chitosan and oat extract; the foaming agent is azodicarbonamide; the crosslinking agent is triallyl isocyanurate.
The application also discloses a preparation method of the antibacterial high-strength EVA foaming shoe material containing the natural extract, which comprises the following steps:
s1: adding the natural extract into a reaction bottle, adding 1 wt% of acetic acid aqueous solution, heating to 65 ℃, stirring for dissolving, introducing nitrogen to remove oxygen, adding an ethyl acrylate monomer and a potassium persulfate initiator, reacting for 1 hour, adding 1 wt% of sodium hydroxide aqueous solution for neutralization, collecting precipitate, washing with water to be neutral, and drying to obtain a modified extract;
s2: uniformly mixing the modified extract with a filler, and carrying out surface treatment on the filler to obtain a mixed filler;
s3: according to the formula (the specific dosage is shown in table 1), respectively adding EVA, a foaming agent, a cross-linking agent, dicumyl peroxide and a mixed filler into a reaction kettle, uniformly mixing at the rotating speed of 150r/min, and then banburying in a banbury mixer for 15min at the temperature of 135 ℃;
s4: and (4) milling and granulating the internally mixed material to obtain the EVA foaming shoe material.
Example 2
The difference from example 1 is that:
a preparation method of an antibacterial high-strength EVA foaming shoe material containing a natural extract comprises the following steps:
s1: adding the natural extract into a reaction bottle, adding a 5wt% acetic acid aqueous solution, heating to 78 ℃, stirring for dissolving, introducing nitrogen to remove oxygen, adding an ethyl acrylate monomer and a potassium persulfate initiator, reacting for 2 hours, adding a 5wt% sodium hydroxide aqueous solution for neutralization, collecting a precipitate, washing with water to be neutral, and drying to obtain a modified extract;
s2: uniformly mixing the modified extract with a filler, and carrying out surface treatment on the filler to obtain a mixed filler;
s3: according to the formula (the specific dosage is shown in table 1), respectively adding EVA, a foaming agent, a cross-linking agent, dicumyl peroxide and a mixed filler into a reaction kettle, uniformly mixing at the rotating speed of 150r/min, and then banburying in a banbury mixer for 20min at the temperature of 130 ℃;
s4: and (4) milling and granulating the internally mixed material to obtain the EVA foaming shoe material.
Example 3
The difference from example 1 is that:
a preparation method of an antibacterial high-strength EVA foaming shoe material containing a natural extract comprises the following steps:
s1: adding the natural extract into a reaction bottle, adding a 3 wt% acetic acid aqueous solution, heating to 70 ℃, stirring for dissolving, introducing nitrogen to remove oxygen, adding an ethyl acrylate monomer and a potassium persulfate initiator, reacting for 1.5h, adding a 3 wt% sodium hydroxide aqueous solution for neutralization, collecting a precipitate, washing with water to be neutral, and drying to obtain a modified extract;
s2: uniformly mixing the modified extract with a filler, and carrying out surface treatment on the filler to obtain a mixed filler;
s3: according to the formula (the specific dosage is shown in table 1), respectively adding EVA, a foaming agent, a cross-linking agent, dicumyl peroxide and a mixed filler into a reaction kettle, uniformly mixing at the rotating speed of 150r/min, and then banburying in a banbury mixer for 18min at the temperature of 135 ℃;
s4: and (4) milling and granulating the internally mixed material to obtain the EVA foaming shoe material.
The amounts of the respective raw materials used in examples 1 to 3 are shown in Table 2, and the unit of the amounts used is kg.
TABLE 1
Example 4
The difference from example 3 is that: 2kg of dodecyl dimethyl benzyl ammonium chloride and 11kg of polyacrylamide are mixed uniformly in advance, and then added into S3 to be mixed with other raw materials uniformly.
Example 5
The difference from example 3 is that: 4kg of dodecyl dimethyl benzyl ammonium chloride and 17kg of polyacrylamide are mixed uniformly in advance, and then added into S3 to be mixed uniformly with other raw materials.
Example 6
The difference from example 5 is that: the polyacrylamide was replaced with an equal amount of dodecyldimethylbenzylammonium chloride.
Example 7
The difference from example 5 is that: the same amount of polyacrylamide is used to replace dodecyl dimethyl benzyl ammonium chloride.
Example 8
The difference from example 3 is that: the natural extract is prepared from the following components in a mass ratio of 1: 1.1, mixing the chitosan and the oat extract.
Example 9
The difference from example 8 is that: the chitosan has an average molecular weight of 55 w.
Example 10
The difference from example 8 is that: the chitosan has an average molecular weight of 20 w.
Example 11
The difference from example 3 is that: the natural extract is prepared from the following components in a mass ratio of 1: 1.3, mixing chitosan and oat extract; the average molecular weight of the chitosan is 80 w; the filler is prepared from calcium carbonate and kaolin according to the mass ratio of 1.2: 2, mixing; the foaming agent is prepared by mixing azodicarbonamide and barium azodicarboxylate in a mass ratio of 1.5: 4.
Comparative example 1
The difference from example 3 is that: the natural extract was not modified in S1.
Comparative example 2
The difference from example 3 is that: the same amount of licorice extract was used in place of chitosan.
Comparative example 3
The difference from example 3 is that: kaolin and calcium carbonate were replaced with equal amounts of talc.
Comparative example 4
The difference from example 3 is that:
an antibacterial high-strength EVA foaming shoe material containing natural extracts is prepared from the following raw materials in parts by weight: EVA85 kg; 5kg of natural extract; 3kg of foaming agent; 6kg of cross-linking agent; 3kg of dicumyl peroxide; 15kg of filler.
Comparative example 5
The difference from example 3 is that:
an antibacterial high-strength EVA foaming shoe material containing natural extracts is prepared from the following raw materials in parts by weight: EVA165 kg; 31kg of natural extract; 16kg of foaming agent; 4kg of cross-linking agent; 2kg of dicumyl peroxide; 17kg of filler.
Experiment 1
According to FT/Z73023-2006, the experiment respectively detects the bacteriostasis rate (%) of the EVA foamed shoe material prepared in the above embodiments and comparative examples, and the higher the bacteriostasis rate is, the better the antibacterial performance of the EVA foamed shoe material is.
Meanwhile, after the EVA foamed shoe materials prepared in the above examples and comparative examples are respectively soaped for 10 times, the bacteriostasis rate is detected, the concentration of the soaping is 20%, and the times of water washing are 20 times. And then calculating the antibacterial change rate (%) before and after 10 soaping, wherein the smaller the change rate is, the longer the antibacterial effect of the EVA foamed shoe material is.
The bacteria inhibition change rate (%) (bacteria inhibition rate before 10 times of soaping-bacteria inhibition rate after 10 times of soaping)/bacteria inhibition rate before 10 times of soaping
Experiment 2
In the experiment, according to GB/T1040-92 Plastic tensile property test methods, the tensile strength (MPa) of the EVA foamed shoe material prepared in the above examples and comparative examples is respectively detected, and the higher the tensile strength is, the better the mechanical strength of the EVA foamed shoe material is.
Experiment 3
An experimenter visually observes that in the process of preparing the EVA foaming shoe material, the filler subjected to the surface treatment of the modified extract is easy to delaminate in a system.
The above experimental data are shown in Table 2.
TABLE 2
Comparing the data of comparative examples 1-3 in the table 2 with that of example 3 respectively, wherein the natural extract in the comparative example 1 is not modified, the same amount of licorice extract is used for replacing chitosan in the comparative example 2, the same amount of talcum powder is used for replacing kaolin and calcium carbonate in the comparative example 3, and the bacteriostatic ratios of the EVA foamed shoe materials in the comparative examples 1-3 are basically approximate; in the embodiment 3, at least two of calcium carbonate, kaolin and magnesium stearate are used as fillers, and then the modified natural extract is matched to pretreat the fillers, compared with the comparative examples 1-3, the antibacterial rate of the EVA foaming shoe material in the embodiment 3 is increased from about 80% to 92.1% before soaping for 10 times, and the antibacterial change rate is reduced from about 12% to 2.2%, which shows that the at least two of calcium carbonate, kaolin and magnesium stearate are used as fillers, and then the modified natural extract is matched to pretreat the fillers, so that the antibacterial performance of the EVA foaming shoe material is improved, the antibacterial durability of the EVA foaming shoe material is improved, and the service life of the EVA foaming shoe material is prolonged.
According to the data analysis of the examples 4-7 and the example 3 in the table 2, the example 6 adds the dodecyl dimethyl benzyl ammonium chloride on the basis of the example 3, and the bacteriostatic change rate of the EVA foaming shoe material is 2.4 percent and is basically close to the example 3; example 7 is based on example 3, polyacrylamide is newly added, the bacteriostatic rate of the EVA foamed shoe material is 88.7% before 10 times of soaping, the bacteriostatic change rate of the EVA foamed shoe material is 1.0%, whereas in example 3, the bacteriostatic rate of the EVA foamed shoe material is 92.1% before 10 times of soaping, the bacteriostatic change rate of the EVA foamed shoe material is 2.2%, and example 7 is compared with example 3, the bacteriostatic rate is reduced by 3.4% before 10 times of soaping, the bacteriostatic change rate is reduced by 1.2%, which indicates that adding polyacrylamide is beneficial to improving the bacteriostatic durability of the EVA foamed shoe material, but may affect the bacteriostatic effect of the EVA foamed shoe material. The filler subjected to surface treatment by the modified extract is easy to delaminate in a system, so that the filler cannot be well mixed with other raw materials uniformly, and the antibacterial performance of the EVA foamed shoe material is reduced.
However, in example 5, the dodecyl dimethyl benzyl ammonium chloride and the polyacrylamide are added simultaneously on the basis of example 3, the bacteriostasis rate of the EVA foamed shoe material is 98.6% before 10 times of soaping, and the bacteriostasis change rate is 1.5%, compared with example 3, the bacteriostasis rate of the EVA foamed shoe material in example 5 before 10 times of soaping is improved by 6.5%, and the bacteriostasis change rate is reduced by 0.7%, which indicates that the dodecyl dimethyl benzyl ammonium chloride and the polyacrylamide are added simultaneously to cooperate with each other, so that not only the bacteriostasis performance of the EVA foamed shoe material is improved, but also the washing fastness of the EVA foamed shoe material is enhanced, and thus the antibacterial performance of the EVA foamed shoe material can be maintained for a longer time, which is beneficial to prolonging the service life of the EVA foamed shoe material.
As can be seen from a comparison of the data from example 8 to example 3, example 8 differs from example 3 in that: in example 8, the natural extract adopts the chitosan and the oat extract in a specific ratio to be matched with each other, the bacteriostasis rate of the EVA foaming shoe material before 10 times of soaping is 95.2%, and the bacteriostasis change rate is 0.8%, compared with example 3, the bacteriostasis rate is improved by 3.1% before 10 times of soaping, and the bacteriostasis change rate is reduced by 1.4%, which indicates that the natural extract adopts the chitosan and the oat extract in a specific ratio to be matched with each other, which is beneficial to improving the antibacterial performance of the EVA foaming shoe material, and simultaneously, the washing fastness of the EVA foaming shoe material is enhanced, so that the antibacterial durability of the EVA foaming shoe material is improved.
Based on a comparison of the data from examples 9-10 with example 8, example 9 differs from example 8 in that: in example 9, the average molecular weight of chitosan is 55w, the bacteriostatic rate of the EVA foamed shoe material before 10 soaping times is 96.5%, the bacteriostatic rate of the EVA foamed shoe material before 10 soaping times is 95.2%, and in example 8, compared with example 8, the bacteriostatic rate of the EVA foamed shoe material before 10 soaping times is improved by 1.3%, which indicates that the chitosan adopts the average molecular weight in a specific range, which is beneficial to improving the antibacterial performance of the EVA foamed shoe material.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (8)
1. An antibacterial high-strength EVA foaming shoe material containing natural extracts is characterized in that: the feed is prepared from the following raw materials in parts by weight:
110-150 parts of EVA; 14-22 parts of natural extracts; 6-12 parts of a foaming agent; 1-2 parts of a crosslinking agent; 0.5-1 part of dicumyl peroxide; 5-9 parts of a filler;
the filler is at least two of calcium carbonate, kaolin and magnesium stearate;
the natural extract is one or more of chitosan, oat extract and cinnamon extract;
the filler is pretreated by natural extracts;
the natural extract is modified in advance by the following method: adding the natural extract into a reaction bottle, adding 1-5wt% of acetic acid aqueous solution, heating to 65-78 ℃, stirring for dissolving, introducing nitrogen to remove oxygen, adding an ethyl acrylate monomer and a potassium persulfate initiator, reacting for 1-2h, adding 1-5wt% of sodium hydroxide aqueous solution for neutralization, collecting precipitate, washing with water to neutrality, and drying to obtain the modified extract.
2. The antibacterial high-strength EVA foaming shoe material containing natural extracts of claim 1, which is characterized in that: the EVA foaming shoe material also comprises the following raw materials in parts by weight:
2-4 parts of dodecyl dimethyl benzyl ammonium chloride;
11-17 parts of polyacrylamide.
3. The antibacterial high-strength EVA foaming shoe material containing natural extracts of claim 1, which is characterized in that: the natural extract is prepared from the following components in a mass ratio of 1: (1.1-1.3) chitosan and oat extract.
4. The antibacterial high-strength EVA foaming shoe material containing natural extracts of claim 3, wherein: the chitosan has an average molecular weight of 55-80 w.
5. The antibacterial high-strength EVA foamed shoe material containing natural extracts of claim 1, wherein: the filler is prepared from calcium carbonate and kaolin according to the mass ratio of (1.2-2): 2, mixing the components.
6. The antibacterial high-strength EVA foamed shoe material containing natural extracts of claim 1, wherein: the foaming agent is one or more of azodicarbonamide, barium azodicarboxylate, azoaminobenzene and azodiisobutyronitrile.
7. The antibacterial high-strength EVA foaming shoe material containing natural extracts of claim 6, which is characterized in that: the foaming agent is prepared by mixing azodicarbonamide and barium azodicarboxylate in a mass ratio of 1.5: 4.
8. The antibacterial high-strength EVA foamed shoe material containing natural extracts of claim 1, wherein: the crosslinking agent is triallyl isocyanurate.
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| CN110372950A (en) * | 2019-07-24 | 2019-10-25 | 温州市宜和鞋材有限公司 | A kind of antibacterial and mouldproof footwear material and preparation method of shoe pads |
| CN114316339A (en) * | 2021-12-07 | 2022-04-12 | 茂泰(福建)鞋材有限公司 | Antibacterial EVA (ethylene-vinyl acetate copolymer) foamed sole and preparation method thereof |
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| CN110372950A (en) * | 2019-07-24 | 2019-10-25 | 温州市宜和鞋材有限公司 | A kind of antibacterial and mouldproof footwear material and preparation method of shoe pads |
| CN114316339A (en) * | 2021-12-07 | 2022-04-12 | 茂泰(福建)鞋材有限公司 | Antibacterial EVA (ethylene-vinyl acetate copolymer) foamed sole and preparation method thereof |
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