CN112500618A - Natural rubber antibacterial insole containing graphene additive - Google Patents
Natural rubber antibacterial insole containing graphene additive Download PDFInfo
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- CN112500618A CN112500618A CN202011461098.2A CN202011461098A CN112500618A CN 112500618 A CN112500618 A CN 112500618A CN 202011461098 A CN202011461098 A CN 202011461098A CN 112500618 A CN112500618 A CN 112500618A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 57
- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 32
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 32
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 32
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 29
- 239000000654 additive Substances 0.000 title claims abstract description 15
- 230000000996 additive effect Effects 0.000 title claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 9
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 229960001484 edetic acid Drugs 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 239000004088 foaming agent Substances 0.000 claims abstract description 5
- 230000009967 tasteless effect Effects 0.000 claims abstract description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 230000009965 odorless effect Effects 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- -1 sodium alkyl benzene Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 7
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 235000019633 pungent taste Nutrition 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 25
- 239000005060 rubber Substances 0.000 description 25
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 9
- 235000019253 formic acid Nutrition 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 244000052616 bacterial pathogen Species 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000002683 foot Anatomy 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 206010047601 Vitamin B1 deficiency Diseases 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 208000002894 beriberi Diseases 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 201000004647 tinea pedis Diseases 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
- A43B17/003—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined characterised by the material
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
- A43B17/10—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined specially adapted for sweaty feet; waterproof
-
- 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
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- 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
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to the technical field of new materials, in particular to a natural rubber antibacterial insole containing a graphene additive, which comprises the following materials in parts by weight: 25-29 parts of natural rubber, 10-12 parts of ethylene-vinyl acetate copolymer, 8-14 parts of talcum powder, 5-8 parts of graphene oxide, 6-9 parts of tasteless cross-linking agent, 4-8 parts of foaming agent, 3-8 parts of ethylene diamine tetraacetic acid and 3-5 parts of silane coupling agent; the antibacterial insoles need to be soaked in an antibacterial agent for antibacterial treatment; the antibacterial agent includes: isothiazolinone, nano zinc oxide and distilled water. The insole material disclosed by the invention is safe, non-toxic, free of pungent taste, good in mechanical property and capable of effectively preventing the growth and reproduction of bacteria.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a natural rubber antibacterial insole containing a graphene additive.
Background
The shoe yield of China reaches 120 hundred million pairs per year, and common shoe pad materials comprise TPR (thermoplastic rubber-TPR); TPU — thermoplastic polyurethane; ABS-rubber (acrylonitrile-styrene-butadiene high polymer); EVA-ethylene-vinyl acetate copolymer; PVC-polyvinyl chloride, and the like. Traditional shoe materials such as polymerized rubber and the like have good performances such as wear resistance, heat resistance, air tightness, natural aging resistance and the like, but have poor tear resistance, high deformation and heat generation and low crude rubber strength. Some rubbers also have the defects of low temperature resistance, poor ozone resistance, poor electrical insulation, large deformation and heat generation and the like. In order to meet the requirements of practical application, the shoe material needs to be reinforced by adopting a reinforcing agent.
The sweat secretion of people is increased sharply after sports, bacteria in shoes are easy to reproduce at high speed to generate stink, and a series of diseases such as tinea pedis, beriberi and the like can be caused after the sweat is worn, so that the physical and mental health of children is directly influenced. The experimental research separates and identifies 13 strains of bacteria, 5 strains of microzyme and 8 strains of mould from shoes, only a small part of pathogenic bacteria in the bacteria are the same as the common strains of feet of adult patients, a plurality of new pathogenic bacteria appear, and the pathogenic microorganisms can generate certain harm to the feet. Therefore, it is important to perform special antibacterial treatment on shoe materials aiming at new pathogenic bacteria identified in shoes. However, there are few insoles with antibacterial function on the market at present, and the demands of consumers for such insoles cannot be met.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a natural rubber antibacterial insole containing a graphene additive.
The purpose of the invention is realized by the following technical scheme:
a natural rubber antibacterial insole containing graphene additives comprises the following materials in parts by weight: 25-29 parts of natural rubber, 10-12 parts of ethylene-vinyl acetate copolymer, 8-14 parts of talcum powder, 5-8 parts of graphene oxide, 6-9 parts of tasteless cross-linking agent, 4-8 parts of foaming agent, 3-8 parts of ethylene diamine tetraacetic acid and 3-5 parts of silane coupling agent; the antibacterial insoles need to be soaked in an antibacterial agent for antibacterial treatment; the antibacterial agent includes: isothiazolinone, nano zinc oxide and distilled water.
Preferably, the preparation method of the graphene oxide comprises the following steps: potassium permanganate and graphite powder are subjected to oxidation reaction to obtain brown graphite flakes with derived carboxylic groups at the edges and mainly phenolic hydroxyl groups and epoxy groups on the planes, the graphite flake layers are stirred and peeled violently by ultrasound or high shear to form graphene oxide, and the stable graphene oxide is formed in water.
Preferably, the weight ratio of isothiazolinone to nano zinc oxide in the antibacterial agent is 5: 2.
preferably, the antibacterial agent further comprises polyacrylamide or sodium alkyl benzene sulfonate.
Preferably, the molecular weight of the ethylene-vinyl acetate copolymer is 5000-.
Preferably, the odorless crosslinking agent is odorless DCP.
Preferably, the foaming agent is calcium carbonate or sodium bicarbonate.
Preferably, the silane coupling agent is gamma-aminopropyltriethoxysilane.
Preferably, the particle size of the nano zinc oxide is 30-45 nm.
The invention has the beneficial effects that:
according to the invention, graphene oxide is added into natural rubber, and the graphene has excellent mechanical property and thermal conductivity, and the graphene oxide is low in price, so that the problems of poor mechanical property and poor heat resistance of the natural rubber can be effectively solved. According to the invention, gamma-aminopropyltriethoxysilane is used as a silane coupling agent, the interface action between the modified graphene oxide and natural rubber is enhanced, the dispersibility of graphene in natural rubber is improved, and the mechanical property of the shoe material is obviously improved. The invention adopts the nano zinc oxide with the particle size of 30-45nm as the degerming agent, and the degerming agent has a plurality of special properties such as non-toxicity, non-migration, antibacterial property, ultraviolet shielding capability and the like due to small particle size, large specific surface area, surface effect, quantum size effect and the like. By using the characteristics of the leather, shoe materials are treated to obtain the shoe pad and shoe lining leather with antibacterial, mildewproof and deodorizing functions. The superiority of nano zinc oxide makes it a hot spot for people to study and widely apply. The isothiazolinone has the characteristics of strong antibacterial ability, small dosage, low toxicity, good compatibility and broad-spectrum antibacterial property, can generate a synergistic effect with the nano zinc oxide, and obviously improves the sterilization effect and the sterilization durability. Meanwhile, the graphene oxide adopted in the invention also has an antibacterial effect, and can destroy the cell membrane of bacteria, cause the outflow of intracellular substances and kill the bacteria.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to the following.
Example 1
The method for preparing the graphene natural rubber shoe material comprises the following steps:
after oxidation reaction is carried out on 50g of potassium permanganate and 15g of graphite powder, a brown graphite sheet with derived carboxylic acid groups at the edges and mainly phenolic hydroxyl groups and epoxy groups on the plane is obtained, the graphite sheet layer is stirred and peeled violently through high shear to form graphene oxide, and stable graphene oxide is formed in water. Weighing 5 parts of graphene oxide according to parts by weight, putting the graphene oxide into 60 parts of water to prepare a graphene aqueous solution, adding 3 parts of gamma-aminopropyltriethoxysilane into the graphene aqueous solution, and magnetically stirring for 3 hours at 60 ℃ to obtain a modified graphene dispersion solution; 25 parts of natural rubber, 10 parts of ethylene-vinyl acetate copolymer, 8 parts of talcum powder, 5 parts of graphene oxide, 6 parts of odorless DCP, 4 parts of calcium carbonate, 3 parts of ethylene diamine tetraacetic acid and 3 parts of gamma-aminopropyltriethoxysilane, adding the modified graphene dispersion, continuously adding water, stirring to mix uniformly, and mechanically stirring for 20min to obtain a natural latex mixed solution. Preparing a formic acid solution with the mass fraction of 8 wt%, adding the formic acid solution into the natural latex mixed solution, and continuously stirring and demulsifying to obtain raw rubber with the filler content of 20 wt%; soaking the raw rubber in water for 24h to remove formic acid (water needs to be changed for 2-3 times in the middle), and then putting the raw rubber into an oven for drying. Plasticating, mixing and vulcanizing the dried raw rubber; keeping the roll spacing of 0.3cm after mixing, and continuing to open for 8min to ensure that the fillers in the rubber compound are directionally arranged; and then putting the rubber compound into a vulcanizing machine mold in a layer-by-layer stacking mode for vulcanization, finally putting the rubber compound into a degerming agent consisting of 10 parts of isothiazolinone, 4 parts of nano zinc oxide, 50 parts of distilled water and 10 parts of polyacrylamide for soaking for 15min, and drying to obtain the graphene natural rubber composite material.
Example 2
The method for preparing the graphene natural rubber shoe material comprises the following steps:
after oxidation reaction is carried out on 50g of potassium permanganate and 15g of graphite powder, a brown graphite sheet with derived carboxylic acid groups at the edges and mainly phenolic hydroxyl groups and epoxy groups on the plane is obtained, the graphite sheet layer is stirred and peeled violently through high shear to form graphene oxide, and stable graphene oxide is formed in water. Weighing 7 parts of graphene oxide according to parts by weight, putting the graphene oxide into 60 parts of water to prepare a graphene aqueous solution, adding 3 parts of gamma-aminopropyltriethoxysilane into the graphene aqueous solution, and magnetically stirring for 3 hours at 60 ℃ to obtain a modified graphene dispersion solution; 27 parts of natural rubber, 11 parts of ethylene-vinyl acetate copolymer, 11 parts of talcum powder, 6 parts of graphene oxide, 7 parts of odorless DCP, 6 parts of calcium carbonate, 5 parts of ethylene diamine tetraacetic acid and 4 parts of gamma-aminopropyltriethoxysilane, adding the modified graphene dispersion, continuously adding water, stirring to mix uniformly, and mechanically stirring for 20min to obtain a natural latex mixed solution. Preparing a formic acid solution with the mass fraction of 8 wt%, adding the formic acid solution into the natural latex mixed solution, and continuously stirring and demulsifying to obtain raw rubber with the filler content of 20 wt%; soaking the raw rubber in water for 24h to remove formic acid (water needs to be changed for 2-3 times in the middle), and then putting the raw rubber into an oven for drying. Plasticating, mixing and vulcanizing the dried raw rubber; keeping the roll spacing of 0.3cm after mixing, and continuing to open for 8min to ensure that the fillers in the rubber compound are directionally arranged; and then putting the rubber compound into a vulcanizing machine mold in a layer-by-layer stacking mode for vulcanization, finally putting the rubber compound into a degerming agent consisting of 10 parts of isothiazolinone, 4 parts of nano zinc oxide, 50 parts of distilled water and 10 parts of polyacrylamide for soaking for 20min, and drying to obtain the graphene natural rubber composite material.
Example 3
The method for preparing the graphene natural rubber shoe material comprises the following steps:
after oxidation reaction is carried out on 50g of potassium permanganate and 15g of graphite powder, a brown graphite sheet with derived carboxylic acid groups at the edges and mainly phenolic hydroxyl groups and epoxy groups on the plane is obtained, the graphite sheet layer is stirred and peeled violently through high shear to form graphene oxide, and stable graphene oxide is formed in water. Weighing 8 parts of graphene oxide according to parts by weight, putting the graphene oxide into 60 parts of water to prepare a graphene aqueous solution, adding 3 parts of gamma-aminopropyltriethoxysilane into the graphene aqueous solution, and magnetically stirring for 3 hours at 60 ℃ to obtain a modified graphene dispersion solution; 29 parts of natural rubber, 12 parts of ethylene-vinyl acetate copolymer, 14 parts of talcum powder, 8 parts of graphene oxide, 9 parts of odorless DCP, 8 parts of sodium bicarbonate, 3-8 parts of ethylene diamine tetraacetic acid and 5 parts of gamma-aminopropyltriethoxysilane, adding the modified graphene dispersion, continuously adding water, stirring to mix uniformly, and mechanically stirring for 20min to obtain a natural latex mixed solution. Preparing a formic acid solution with the mass fraction of 8 wt%, adding the formic acid solution into the natural latex mixed solution, and continuously stirring and demulsifying to obtain raw rubber with the filler content of 20 wt%; soaking the raw rubber in water for 24h to remove formic acid (water needs to be changed for 2-3 times in the middle), and then putting the raw rubber into an oven for drying. Plasticating, mixing and vulcanizing the dried raw rubber; keeping the roll spacing of 0.3cm after mixing, and continuing to open for 8min to ensure that the fillers in the rubber compound are directionally arranged; and then putting the mixed rubber into a vulcanizing machine mold in a layer-by-layer stacking mode for vulcanization, finally putting the mixed rubber into a degerming agent consisting of 10 parts of isothiazolinone, 4 parts of nano zinc oxide, 50 parts of distilled water and 10 parts of sodium alkyl benzene sulfonate for soaking for 25min, and drying to obtain the graphene natural rubber composite material.
The graphene natural rubber materials prepared in examples 1 to 3 were tested for thermal conductivity, tensile strength, and elongation at break and tested for bacteria, and the following results are shown in table 1 below:
test results
| Item | Example 1 | Example 2 | Example 3 |
| Thermal conductivity W/m-1K-1 | 0.52 | 0.48 | 0.46 |
| Tensile strength MPa | 22.38 | 24.12 | 21.52 |
| Elongation at break% | 624.1 | 634.4 | 635.2 |
| Antibacterial rate of Escherichia coli% | 99.6 | 99.4 | 99.5 |
| Staphylococcus aureus% | 99.5 | 99.6 | 99.6 |
TABLE 1
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A natural rubber antibacterial insole containing graphene additives is characterized by comprising the following materials in parts by weight: 25-29 parts of natural rubber, 10-12 parts of ethylene-vinyl acetate copolymer, 8-14 parts of talcum powder, 5-8 parts of graphene oxide, 6-9 parts of tasteless cross-linking agent, 4-8 parts of foaming agent, 3-8 parts of ethylene diamine tetraacetic acid and 3-5 parts of silane coupling agent; the antibacterial insoles need to be soaked in an antibacterial agent for antibacterial treatment; the antibacterial agent includes: isothiazolinone, nano zinc oxide and distilled water.
2. The natural rubber antibacterial insole containing the graphene additive according to claim 1, wherein the preparation method of the graphene oxide comprises the following steps: potassium permanganate and graphite powder are subjected to oxidation reaction to obtain brown graphite flakes with derived carboxylic groups at the edges and mainly phenolic hydroxyl groups and epoxy groups on the planes, the graphite flake layers are stirred and peeled violently by ultrasound or high shear to form graphene oxide, and the stable graphene oxide is formed in water.
3. The natural rubber antibacterial insole containing the graphene additive according to claim 2, wherein the weight ratio of isothiazolinone to nano zinc oxide in the antibacterial agent is 5: 2.
4. the natural rubber antibacterial insole containing graphene additives according to claim 1, wherein the antibacterial agent further comprises polyacrylamide or sodium alkyl benzene sulfonate.
5. The natural rubber antibacterial insole containing graphene additive as claimed in claim 1, wherein the molecular weight of the ethylene-vinyl acetate copolymer is 5000-.
6. The natural rubber antibacterial insole containing graphene additives according to claim 1, wherein the odorless cross-linking agent is odorless DCP.
7. The natural rubber antibacterial insole containing the graphene additive according to claim 1, wherein the foaming agent is calcium carbonate or sodium bicarbonate.
8. The natural rubber antibacterial insole containing the graphene additive according to claim 1, wherein the silane coupling agent is γ -aminopropyltriethoxysilane.
9. The natural rubber antibacterial insole containing the graphene additive according to claim 1, wherein the nano zinc oxide has a particle size of 30-45 nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337017A (en) * | 2021-05-24 | 2021-09-03 | 福建五持恒科技发展有限公司 | Graphene rubber polymer far infrared composite foaming material |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407593A (en) * | 2007-10-10 | 2009-04-15 | 邱晴棋 | Rubber foaming body and use of rice hull active carbon as rubber foaming additive |
| CN103332670A (en) * | 2013-06-21 | 2013-10-02 | 重庆交通大学 | Method for preparing graphene oxide |
| CN103627239A (en) * | 2013-12-12 | 2014-03-12 | 李泽国 | Antibacterial, mildew-proof and algae-proof auxiliary of aqueous paint and preparation method thereof |
| CN103951856A (en) * | 2014-05-23 | 2014-07-30 | 徐建先 | Shoemaking material, shoe soles and shoe pads prepared from material and preparation method of material |
| WO2016184324A1 (en) * | 2015-05-18 | 2016-11-24 | 宝峰时尚国际控股有限公司 | Use of photocatalytic composite material, antibacterial and deodorant insoles, shoes, and preparation method thereof |
| CN106432818A (en) * | 2015-08-13 | 2017-02-22 | 株式会社东庚化学 | Composition of foaming insole and manufacturing method of foaming insole using the same |
| CN107100016A (en) * | 2017-03-08 | 2017-08-29 | 四川大学 | A kind of sandwich processing method of antibacterial non-natural leather |
| CN107674293A (en) * | 2016-08-01 | 2018-02-09 | 福建新峰二维材料科技有限公司 | A kind of antibacterial bacteriostatic foamed shoe-pad and preparation method thereof |
| CN107985155A (en) * | 2017-11-15 | 2018-05-04 | 周荣 | A kind of preparation method of high antibacterial antiskid automobile foot pad |
| JP2020132551A (en) * | 2019-02-15 | 2020-08-31 | 学校法人帝京大学 | Antimicrobial composition and insole containing the same |
| EP3744206A1 (en) * | 2019-05-24 | 2020-12-02 | Siretessile Srl | Improved multilayer for insole |
-
2020
- 2020-12-11 CN CN202011461098.2A patent/CN112500618A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407593A (en) * | 2007-10-10 | 2009-04-15 | 邱晴棋 | Rubber foaming body and use of rice hull active carbon as rubber foaming additive |
| CN103332670A (en) * | 2013-06-21 | 2013-10-02 | 重庆交通大学 | Method for preparing graphene oxide |
| CN103627239A (en) * | 2013-12-12 | 2014-03-12 | 李泽国 | Antibacterial, mildew-proof and algae-proof auxiliary of aqueous paint and preparation method thereof |
| CN103951856A (en) * | 2014-05-23 | 2014-07-30 | 徐建先 | Shoemaking material, shoe soles and shoe pads prepared from material and preparation method of material |
| WO2016184324A1 (en) * | 2015-05-18 | 2016-11-24 | 宝峰时尚国际控股有限公司 | Use of photocatalytic composite material, antibacterial and deodorant insoles, shoes, and preparation method thereof |
| CN106432818A (en) * | 2015-08-13 | 2017-02-22 | 株式会社东庚化学 | Composition of foaming insole and manufacturing method of foaming insole using the same |
| CN107674293A (en) * | 2016-08-01 | 2018-02-09 | 福建新峰二维材料科技有限公司 | A kind of antibacterial bacteriostatic foamed shoe-pad and preparation method thereof |
| CN107100016A (en) * | 2017-03-08 | 2017-08-29 | 四川大学 | A kind of sandwich processing method of antibacterial non-natural leather |
| CN107985155A (en) * | 2017-11-15 | 2018-05-04 | 周荣 | A kind of preparation method of high antibacterial antiskid automobile foot pad |
| JP2020132551A (en) * | 2019-02-15 | 2020-08-31 | 学校法人帝京大学 | Antimicrobial composition and insole containing the same |
| EP3744206A1 (en) * | 2019-05-24 | 2020-12-02 | Siretessile Srl | Improved multilayer for insole |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337017A (en) * | 2021-05-24 | 2021-09-03 | 福建五持恒科技发展有限公司 | Graphene rubber polymer far infrared composite foaming material |
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