CN113698710B - Wear-resistant antibacterial shoe material and preparation method thereof - Google Patents
Wear-resistant antibacterial shoe material and preparation method thereof Download PDFInfo
- Publication number
- CN113698710B CN113698710B CN202111159771.1A CN202111159771A CN113698710B CN 113698710 B CN113698710 B CN 113698710B CN 202111159771 A CN202111159771 A CN 202111159771A CN 113698710 B CN113698710 B CN 113698710B
- Authority
- CN
- China
- Prior art keywords
- parts
- shoe material
- wear
- silicon nitride
- nano silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a wear-resistant and antibacterial shoe material and a preparation method thereof, belonging to the technical field of shoe materials, and comprising the following raw materials: 5 to 10 parts of styrene-ethylene butene polymer, 45 to 70 parts of chlorinated butyl rubber, 2 to 5 parts of calcium sulfate whisker, 3 to 5 parts of graphene oxide, 2 to 10 parts of nano silicon nitride, 0.5 to 3 parts of stearic acid, 3 to 5 parts of nano zinc oxide, 12 to 16 parts of carbon black, 0.5 to 5 parts of coupling agent, 2 to 10 parts of anion additive, 0.5 to 2.5 parts of anti-aging agent, 0.4 to 2.5 parts of vulcanization accelerator and 1.0 to 2.0 parts of sulfur. The nano silicon nitride in the shoe material provided by the invention has higher surface hardness and self-lubricity, so that the wear resistance of the shoe material is improved, and the negative ion additive has an antibacterial and bacteriostatic effect, and the components cooperate to ensure that the shoe material has excellent wear resistance and antibacterial property. The results of the examples show that the wear volume of the shoe material provided by the invention is 30mm 3 。
Description
Technical Field
The invention belongs to the technical field of shoe materials, and particularly relates to a wear-resistant antibacterial shoe material and a preparation method thereof.
Background
Shoes are indispensable articles for daily use of people's trip, except having traditional convenient and practical characteristics, pay more attention to comfortable, pleasing to the eye and development of functionality, along with the development of age, people's requirement to shoes is higher and higher.
In general, shoes have poor wear resistance and seriously affect the service life of the shoes, and the wear volume of the shoe materials prepared in the prior art, such as the invention patent with publication number of CN104910507A, reaches 58mm 3 The method comprises the steps of carrying out a first treatment on the surface of the And the general shoes have no antibacterial performance, and the health problem of feet is easily caused when the shoes are worn for a long time.
Accordingly, there is a need for a shoe material that is excellent in abrasion resistance and antibacterial properties.
Disclosure of Invention
The invention aims to provide wear-resistant and antibacterial shoe materials and a preparation method thereof. The shoe material provided by the invention has excellent wear resistance and antibacterial performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a wear-resistant antibacterial shoe material which is prepared from the following raw materials in parts by weight: 5 to 10 parts of styrene-ethylene butene polymer, 45 to 70 parts of chlorinated butyl rubber, 2 to 5 parts of calcium sulfate whisker, 3 to 5 parts of graphene oxide, 2 to 10 parts of nano silicon nitride, 0.5 to 3 parts of stearic acid, 3 to 5 parts of nano zinc oxide, 12 to 16 parts of carbon black, 0.5 to 5 parts of coupling agent, 2 to 10 parts of anion additive, 0.5 to 2.5 parts of anti-aging agent, 0.4 to 2.5 parts of vulcanization accelerator and 1.0 to 2.0 parts of sulfur.
Preferably, the particle size of the nano silicon nitride is 1-50 nm.
Preferably, the particle size of the nano zinc oxide is 40-70 nm.
Preferably, the coupling agent comprises a silane coupling agent or a titanate coupling agent.
Preferably, the negative ion additive comprises opal powder and medical stone powder.
Preferably, the mass ratio of the opal powder to the medical stone powder is 1: (0.1-1).
Preferably, the anti-aging agent comprises N, N-bis (β -naphthyl) p-phenylenediamine or N, N-bis (2-naphthyl) p-phenylenediamine.
Preferably, the vulcanization accelerator comprises a thiuram accelerator, a sulfenamide accelerator or a dithiocarbamate accelerator.
The invention also provides a preparation method of the wear-resistant antibacterial shoe material, which comprises the following steps:
(1) Mixing nano silicon nitride with a coupling agent and acetone, and performing modification treatment to obtain modified nano silicon nitride;
(2) Mixing the modified nano silicon nitride obtained in the step (1) with a styrene-ethylene butene polymer, chlorinated butyl rubber, calcium sulfate whisker, graphene oxide, stearic acid, nano zinc oxide, carbon black and a negative ion additive, and mixing to obtain a premix;
(3) Mixing the premix obtained in the step (2) with an anti-aging agent, a vulcanization accelerator and sulfur, and pressing after open milling to obtain a sheet;
(4) And (3) vulcanizing the sheet obtained in the step (3) to obtain the wear-resistant antibacterial shoe material.
Preferably, the temperature of the vulcanization in the step (4) is 120-140 ℃, and the pressure of the vulcanization is 10-15 MPa.
The invention provides a wear-resistant antibacterial shoe material which is prepared from the following raw materials in parts by weight: 5 to 10 parts of styrene-ethylene butene polymer, 45 to 70 parts of chlorinated butyl rubber, 2 to 5 parts of calcium sulfate whisker, 3 to 5 parts of graphene oxide, 2 to 10 parts of nano silicon nitride, 0.5 to 3 parts of stearic acid, 3 to 5 parts of nano zinc oxide, 12 to 16 parts of carbon black, 0.5 to 5 parts of coupling agent, 2 to 10 parts of anion additive, 0.5 to 2.5 parts of anti-aging agent, 0.4 to 2.5 parts of vulcanization accelerator and 1.0 to 2.0 parts of sulfur. The styrene-ethylene butylene polymer in the shoe material provided by the invention can improve the elasticity and toughness of the chlorinated butyl rubber; the calcium sulfate whisker and the graphene oxide can enhance the hardness and comfort of the shoe material and improve the wear resistance; the nano silicon nitride has larger surface hardness and self-lubricating property, and further improves the wear resistance of the shoe material; the coupling agent can improve the compatibility of the inorganic material and the rubber; the negative ion additive can release negative ions, adsorb toxic and harmful gases and elements, and has the functions of resisting and inhibiting bacteria and removing odor; the dosage of each component is controlled, and the components cooperate to ensure that the shoe material has excellent performanceAbrasion resistance and antibacterial properties. The results of the examples show that the shoe materials provided by the invention have a wear volume of 30mm when tested in accordance with DIN 53516 GB 9867 3 。
Detailed Description
The invention provides a wear-resistant antibacterial shoe material which is prepared from the following raw materials in parts by weight: 5 to 10 parts of styrene-ethylene butene polymer, 45 to 70 parts of chlorinated butyl rubber, 2 to 5 parts of calcium sulfate whisker, 3 to 5 parts of graphene oxide, 2 to 10 parts of nano silicon nitride, 0.5 to 3 parts of stearic acid, 3 to 5 parts of nano zinc oxide, 12 to 16 parts of carbon black, 0.5 to 5 parts of coupling agent, 2 to 10 parts of anion additive, 0.5 to 2.5 parts of anti-aging agent, 0.4 to 2.5 parts of vulcanization accelerator and 1.0 to 2.0 parts of sulfur.
The source of each of the components is not particularly limited, and commercially available products known to those skilled in the art may be used unless otherwise specified.
The raw materials for preparing the wear-resistant antibacterial shoe material comprise 5-10 parts by weight of styrene-ethylene butylene polymer, preferably 6-9 parts by weight, and more preferably 7-8 parts by weight. In the invention, the styrene-ethylene butylene polymer can improve the elasticity and toughness of the rubber shoe material and improve the comfort and performance of the shoe material. The invention limits the usage amount of the styrene-ethylene butylene polymer in the above range, so that the shoe material has better elasticity and toughness.
The raw materials for preparing the wear-resistant antibacterial shoe material comprise 45-70 parts of chlorinated butyl rubber, preferably 50-65 parts, and more preferably 60 parts, based on 5-10 parts of styrene-ethylene butylene polymer. In the present invention, the chlorinated butyl rubber is used as a main material of a shoe material. The invention limits the dosage of the chlorinated butyl rubber within the range, so that the shoe material is soft and elastic, and has shockproof performance and the like. The invention limits the dosage of the chlorinated butyl rubber within the range, so that the shoe material has better elasticity and shock resistance.
The raw materials for preparing the wear-resistant and bacteriostatic shoe material comprise 2-5 parts of calcium sulfate whisker, preferably 3-4 parts, by weight of 5-10 parts of styrene-ethylene butylene polymer. In the invention, the calcium sulfate whisker is a fibrous monocrystal, has better performances of wear resistance, high toughness, high strength and the like, and can be used as a shoe material reinforcing and toughening material to improve the performance of the shoe material. The invention limits the dosage of the calcium sulfate whisker in the range, can be uniformly dispersed in the shoe material, and further improves the wear resistance, strength and toughness of the shoe material.
The raw materials for preparing the wear-resistant antibacterial shoe material comprise 3-5 parts of graphene oxide, preferably 4 parts, based on the mass of 5-10 parts of styrene-ethylene butylene polymer. In the invention, the graphene oxide has large specific surface area and high mechanical strength, contains a large number of polar groups on the surface, can form good interface interaction with the polymer, improves the performance of the shoe material, and has certain antibacterial performance. The invention limits the dosage of the graphene oxide within the range, can be uniformly dispersed in the shoe material, and further improves the strength and the antibacterial property of the shoe material.
The raw materials for preparing the wear-resistant and antibacterial shoe material comprise 2-10 parts of nano silicon nitride, preferably 3-9 parts, more preferably 4-8 parts and most preferably 5-7 parts, calculated by the mass of the styrene-ethylene butylene polymer being 5-10 parts. In the invention, the nano silicon nitride has larger surface hardness and self-lubricity, and can improve the wear resistance of the shoe material. The invention limits the dosage of the nano silicon nitride in the range, can be uniformly dispersed in the shoe material, and further improves the wear resistance of the shoe material.
In the present invention, the particle diameter of the nano silicon nitride is preferably 1 to 50nm, more preferably 10 to 40nm, and most preferably 20 to 30nm. The invention limits the grain diameter of the nanometer silicon nitride in the range, can improve the specific surface area, can be uniformly dispersed in the shoe material, and further improves the performance of the shoe material.
The raw materials for preparing the wear-resistant antibacterial shoe material comprise 0.5 to 3 parts of stearic acid, preferably 1 to 2.5 parts of stearic acid, and more preferably 1.5 to 2 parts of stearic acid, calculated by the mass of the styrene-ethylene butylene polymer of 5 to 10 parts. In the invention, the stearic acid has softening and plasticizing effects, can reduce the viscosity of the shoe material, improve the processing performance and the plasticity of the shoe material, and can be used as an external lubricant to avoid adhesion between the shoe material and equipment in the processing process; meanwhile, the nano zinc oxide has a synergistic effect with nano zinc oxide, so that the vulcanization efficiency and the vulcanization crosslinking density are improved, and the strength and the ageing resistance of the shoe material are further improved. The invention limits the dosage of stearic acid in the above range, which can make the shoe material have better processing property and vulcanization crosslinking density, and further improve the performance of the shoe material.
The raw materials for preparing the wear-resistant antibacterial shoe material comprise 3-5 parts of nano zinc oxide, preferably 4 parts, based on the mass of 5-10 parts of styrene-ethylene butylene polymer. In the invention, the nano zinc oxide can improve the wear resistance, tear resistance and tensile strength of the shoe material, can be used as a vulcanization accelerator, has a synergistic effect with stearic acid, improves the vulcanization crosslinking density and improves the performance of the shoe material. The invention limits the dosage of the nano zinc oxide within the range, and can further improve the performances of wear resistance, tear resistance and the like of the shoe material.
In the present invention, the particle diameter of the nano zinc oxide is preferably 40 to 70nm, more preferably 50 to 60nm. The particle size of the nano zinc oxide is limited in the range, so that the nano zinc oxide can be uniformly dispersed in the shoe material, and the performance of the shoe material is further improved.
The raw materials for preparing the wear-resistant antibacterial shoe material comprise 12-16 parts of carbon black, preferably 13-15 parts of carbon black and more preferably 14 parts of carbon black, calculated by 5-10 parts of styrene-ethylene butylene polymer. In the invention, the carbon black is used as a rubber reinforcing agent, so that the rubber strength can be improved, and the wear resistance of the rubber can be enhanced. The present invention can further improve the strength and wear resistance of the shoe material by limiting the amount of carbon black to the above-described range.
The raw materials for preparing the wear-resistant antibacterial shoe material comprise 0.5 to 5 parts of coupling agent, preferably 1 to 4 parts, and more preferably 2 to 3 parts, based on 5 to 10 parts of styrene-ethylene butylene polymer. The invention limits the dosage of the coupling agent within the above range, can improve the compatibility of inorganic components and organic components, and further improves the performance of the shoe material.
In the present invention, the coupling agent preferably includes a silane coupling agent or a titanate coupling agent, more preferably a silane coupling agent.
The raw materials for preparing the wear-resistant and bacteriostatic shoe material comprise 2-10 parts of anion additive, preferably 3-9 parts, more preferably 4-8 parts and most preferably 5-7 parts, calculated by 5-10 parts of styrene-ethylene butylene polymer. In the invention, the negative ion additive can release negative ions, adsorb toxic and harmful gases and elements, and has the functions of resisting and inhibiting bacteria and removing odor. The invention limits the dosage of the negative ion additive in the above range, and can further improve the antibacterial and deodorant performances of the shoe material.
In the invention, the anion additive is preferably opal powder and medical stone powder; the mass ratio of the opal powder to the medical stone powder is preferably 1: (0.1 to 1), more preferably 1: (0.3 to 0.8), most preferably 1: (0.5-0.6). The invention limits the types and the dosage of the negative ion additive in the range, can better absorb harmful gases and elements, keep feet fresh, remove odor, and better disperse in shoe materials, thereby further improving the performance of the shoe materials.
In the present invention, the particle diameter of the negative ion additive is preferably 0.2 to 1. Mu.m, more preferably 0.3 to 0.8. Mu.m, and most preferably 0.5 to 0.6. Mu.m. The particle size of the negative ion additive is limited in the range, so that the negative ion additive has larger specific surface area, better adsorbs harmful gases and can be more uniformly dispersed in the shoe material.
The raw materials for preparing the wear-resistant antibacterial shoe material comprise 0.5-2.5 parts of anti-aging agent, preferably 1-2 parts, more preferably 1.5 parts, based on 5-10 parts of styrene-ethylene butylene polymer. The invention limits the usage amount of the anti-aging agent within the range, can improve the anti-aging performance of the shoe material and prolong the service life of the shoe material.
In the present invention, the antioxidant preferably includes N, N-di (β -naphthyl) p-phenylenediamine or N, N-di (2-naphthyl) p-phenylenediamine. The present invention can further improve the anti-aging performance of the shoe material by limiting the types of the anti-aging agent to the above-described ranges.
The raw materials for preparing the wear-resistant antibacterial shoe material comprise 0.4-2.5 parts of vulcanization accelerator, preferably 0.6-2 parts, more preferably 1-1.5 parts, based on 5-10 parts of styrene-ethylene butylene polymer. The invention limits the dosage of the vulcanization accelerator within the range, can promote the vulcanization of shoe materials, shortens the vulcanization time, improves the vulcanization crosslinking density and further improves the performance of the shoe materials.
In the present invention, the vulcanization accelerator preferably includes a thiuram-type accelerator, a sulfenamide-type accelerator, or a dithiocarbamate-type accelerator.
The raw materials for preparing the wear-resistant antibacterial shoe material comprise 1.0-2.0 parts of sulfur, preferably 1.5 parts of sulfur, calculated by 5-10 parts of styrene-ethylene butylene polymer. The invention limits the dosage of sulfur in the range, and the sulfur is used as the vulcanizing agent, so that the shoe material can be fully vulcanized and crosslinked, the crosslinking density is improved, and the performance of the shoe material is further improved.
The styrene-ethylene butylene polymer in the shoe material provided by the invention can improve the elasticity and toughness of the chlorinated butyl rubber; the calcium sulfate whisker and the graphene oxide can enhance the hardness and comfort of the shoe material and improve the wear resistance; the nano silicon nitride has larger surface hardness and self-lubricating property, and further improves the wear resistance of the shoe material; the coupling agent can improve the compatibility of the inorganic material and the rubber; the negative ion additive can release negative ions, adsorb toxic and harmful gases and elements, and has the functions of resisting and inhibiting bacteria and removing odor; the dosages of the components are controlled, and the components act synergistically, so that the shoe material has excellent performances such as wear resistance, antibacterial property and the like.
The invention also provides a preparation method of the wear-resistant antibacterial shoe material, which comprises the following steps:
(1) Mixing nano silicon nitride with a coupling agent and acetone, and performing modification treatment to obtain modified nano silicon nitride;
(2) Mixing the modified nano silicon nitride obtained in the step (1) with a styrene-ethylene butene polymer, chlorinated butyl rubber, calcium sulfate whisker, graphene oxide, stearic acid, nano zinc oxide, carbon black and a negative ion additive, and mixing to obtain a premix;
(3) Mixing the premix obtained in the step (2) with an anti-aging agent, a vulcanization accelerator and sulfur, and pressing after open milling to obtain a sheet;
(4) And (3) vulcanizing the sheet obtained in the step (3) to obtain the wear-resistant antibacterial shoe material.
The invention mixes the nanometer silicon nitride with the coupling agent and the acetone, and carries out modification treatment to obtain the modified nanometer silicon nitride.
In the present invention, the acetone is used as a solvent for dispersing nano silicon nitride.
In the invention, the volume ratio of the mass of the nano silicon nitride to the acetone is preferably 1g (5-10 mL), more preferably 1 g/8 mL. The invention limits the volume ratio of the mass of the nano silicon nitride to the acetone in the range, so that the nano silicon nitride can be dispersed more uniformly.
The operation of mixing the nano silicon nitride with the coupling agent and the acetone is not particularly limited, and the technical scheme of mixing materials well known to the person skilled in the art can be adopted.
In the present invention, the modification treatment is preferably performed under stirring conditions; the stirring is preferably mechanical stirring; the stirring speed is preferably 500-1000 rpm, more preferably 800rpm; the temperature of the modification treatment is preferably 50 to 100 ℃, more preferably 70 to 80 ℃; the time of the modification treatment is preferably 1 to 3 hours, more preferably 2 hours. In the present invention, the modification treatment is preferably performed under nitrogen. The invention limits the parameters of temperature, time and the like of the modification treatment in the above range, can lead the coupling agent to fully react with the nano silicon nitride and improve the compatibility of the coupling agent with other components.
After the modification treatment is completed, the modified nano silicon nitride is preferably obtained by drying the modified product.
The temperature and time of the drying are not particularly limited, and the acetone can be volatilized completely.
After the modified nano silicon nitride is obtained, the modified nano silicon nitride is mixed with a styrene-ethylene butene polymer, chlorinated butyl rubber, calcium sulfate whisker, graphene oxide, stearic acid, nano zinc oxide, carbon black and an anion additive, and then mixed to obtain a premix.
The invention is not particularly limited in the operation of mixing the modified nano silicon nitride with the styrene-ethylene butene polymer, the chlorinated butyl rubber, the calcium sulfate whisker, the graphene oxide, the stearic acid, the nano zinc oxide, the carbon black and the negative ion additive, and adopts a technical scheme of mixing materials which are well known to those skilled in the art.
In the present invention, the kneading preferably includes banburying and open milling performed sequentially. In the present invention, the time of the banburying is preferably 10 to 20 minutes, more preferably 15 minutes; the temperature of the open mill is preferably 120-160 ℃, more preferably 130-150 ℃; the time of the open mill is preferably 20 to 30 minutes, more preferably 25 minutes. The invention limits the temperature and time of banburying and open milling in the above range, and can ensure that the components are mixed more uniformly.
After the premix is obtained, the premix, the anti-aging agent, the vulcanization accelerator and the sulfur are mixed, and the sheet is obtained by open-mixing and pressing.
The operation of mixing the premix, the anti-aging agent, the vulcanization accelerator and the sulfur is not particularly limited, and the technical scheme of mixing materials which are well known to those skilled in the art can be adopted.
In the invention, the temperature of the open mill is preferably 120-160 ℃, more preferably 130-150 ℃; the time of the open mill is preferably 1 to 10 minutes, more preferably 5 minutes. The invention limits the temperature and time of the open mill in the above range, can uniformly mix the components, and can avoid adverse effect on the performance of the components.
In the present invention, the pressing is preferably performed in an open mill. The pressing operation is not particularly limited, and a technical scheme of pressing a sheet material, which is well known to those skilled in the art, may be adopted.
The thickness of the sheet is not particularly limited, and the sheet can be selected according to actual needs.
After the sheet material is obtained, the sheet material is vulcanized to obtain the wear-resistant antibacterial shoe material.
In the present invention, the temperature of the vulcanization is preferably 120 to 140 ℃, more preferably 130 ℃; the pressure of the vulcanization is preferably 10 to 15MPa, more preferably 12 to 13MPa; the time for the vulcanization is preferably 1 to 10 minutes, more preferably 3 to 7 minutes. The invention limits the temperature, pressure and time of vulcanization within the above ranges, can fully carry out vulcanization, improves the crosslinking density and further improves the performance of the shoe material.
The invention controls the adding sequence of each component, the temperature, time and other technological parameters of the reaction process, so that each component is fully and uniformly mixed for reaction, and the performance of the shoe material is further improved.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The wear-resistant antibacterial shoe material provided by the embodiment is prepared from the following raw materials in parts by weight: 5 parts of styrene-ethylene butene polymer, 45 parts of chlorinated butyl rubber, 2 parts of calcium sulfate whisker, 3 parts of graphene oxide, 2 parts of nano silicon nitride (particle size of 10-30 nm), 0.5 part of stearic acid, 3 parts of nano zinc oxide (particle size of 50-60 nm), 12 parts of carbon black, 5503 parts of silane coupling agent KH, 2 parts of anion additive (the mass ratio of opal powder to medical stone powder is 1:0.5), 1 part of N, N-di (beta-naphthyl) p-phenylenediamine, 0.5 part of thiuram TMTD and 1.0 part of sulfur;
the preparation method comprises the following steps: (1) Mixing nano silicon nitride with a silane coupling agent KH550 and acetone (the mass of the nano silicon nitride and the volume ratio of the acetone are 1g:5 mL), reacting for 2 hours at 70 ℃ under the condition of nitrogen, and then drying to obtain modified nano silicon nitride;
(2) Mixing the modified nano silicon nitride with a styrene-ethylene butylene polymer, chlorinated butyl rubber, calcium sulfate whisker, graphene oxide, stearic acid, nano zinc oxide, carbon black and a negative ion additive, banburying in an internal mixer for 15min, and then carrying out open mill at 140 ℃ for 20min in an open mill to obtain a premix;
(3) Mixing the premix with N, N-di (beta-naphthyl) p-phenylenediamine, thiuram TMTD and sulfur, carrying out open milling at 140 ℃ for 5min, and then rolling into sheets;
(4) Vulcanizing the sheet material at 130 ℃ and 12MPa for 5min to obtain the wear-resistant antibacterial shoe material.
Example 2
The wear-resistant antibacterial shoe material provided by the embodiment is prepared from the following raw materials in parts by weight: 7 parts of styrene-ethylene butene polymer, 60 parts of chlorinated butyl rubber, 3 parts of calcium sulfate whisker, 5 parts of graphene oxide, 4 parts of nano silicon nitride (particle size of 10-30 nm), 2 parts of stearic acid, 4 parts of nano zinc oxide (particle size of 50-60 nm), 13 parts of carbon black, 5504 parts of silane coupling agent KH, 3 parts of anion additive (the mass ratio of opal powder to medical stone powder is 1:0.5), 2 parts of N, N-di (beta-naphthyl) p-phenylenediamine, 1.5 parts of thiuram TMTD and 1.5 parts of sulfur;
the preparation method is the same as in example 1.
Example 3
The wear-resistant antibacterial shoe material provided by the embodiment is prepared from the following raw materials in parts by weight: 10 parts of styrene-ethylene butene polymer, 70 parts of chlorinated butyl rubber, 3 parts of calcium sulfate whisker, 5 parts of graphene oxide, 4 parts of nano silicon nitride (particle size of 10-30 nm), 3 parts of stearic acid, 5 parts of nano zinc oxide (particle size of 50-60 nm), 13 parts of carbon black, 5505 parts of silane coupling agent KH, 3 parts of anion additive (the mass ratio of opal powder to medical stone powder is 1:0.5), 2 parts of N, N-di (beta-naphthyl) p-phenylenediamine, 1.5 parts of thiuram TMTD and 1.5 parts of sulfur;
the preparation method is the same as in example 1.
Comparative example 1
The shoe material provided by the comparative example is prepared from the following raw materials in parts by weight: 10 parts of styrene-ethylene butene polymer, 70 parts of chlorinated butyl rubber, 3 parts of calcium sulfate whisker, 5 parts of graphene oxide, 3 parts of stearic acid, 5 parts of nano zinc oxide (particle size of 50-60 nm), 13 parts of carbon black, 5505 parts of silane coupling agent KH, 3 parts of anion additive (the mass ratio of opal powder to medical stone powder is 1:0.5), 2 parts of N, N-di (beta-naphthyl) p-phenylenediamine, 1.5 parts of thiuram TMTD and 1.5 parts of sulfur;
the preparation method is the same as in example 1.
The shoe materials of examples 1 to 3 and comparative example 1 were subjected to abrasion resistance test according to DIN 53516 GB 9867, and the results are shown in Table 1.
Table 1 abrasion resistance of shoe materials of examples 1 to 3 and comparative example 1
| Abrasion volume (mm) 3 ) | |
| Example 1 | 38 |
| Example 2 | 33 |
| Example 3 | 30 |
| Comparative example 1 | 67 |
As can be seen from Table 1, the wear-resistant and bacteriostatic shoe material provided by the invention has excellent wear resistance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The wear-resistant antibacterial shoe material is prepared from the following raw materials in parts by weight: 5-10 parts of styrene-ethylene butene polymer, 45-70 parts of chlorinated butyl rubber, 2-5 parts of calcium sulfate whisker, 3-5 parts of graphene oxide, 4 parts of nano silicon nitride, 0.5-3 parts of stearic acid, 3-5 parts of nano zinc oxide, 12-16 parts of carbon black, 0.5-5 parts of coupling agent, 2-10 parts of anion additive, 0.5-2.5 parts of anti-aging agent, 0.4-2.5 parts of vulcanization accelerator and 1.0-2.0 parts of sulfur; the particle size of the nano silicon nitride is 1-50 nm; the negative ion additive comprises opal powder and medical stone powder, wherein the mass ratio of the opal powder to the medical stone powder is 1: (0.1-1);
the coupling agent comprises a silane coupling agent or a titanate coupling agent.
2. The wear-resistant and bacteriostatic shoe material according to claim 1, wherein the particle size of the nano zinc oxide is 40-70 nm.
3. A wear resistant, bacteriostatic footwear according to claim 1, wherein said anti-aging agent comprises N, N-bis (β -naphthyl) p-phenylenediamine.
4. A wear resistant, bacteriostatic shoe material according to claim 1, characterized in that said vulcanization accelerator comprises a thiuram accelerator, a sulfenamide accelerator or a dithiocarbamate accelerator.
5. The method for preparing the wear-resistant antibacterial shoe material according to any one of claims 1 to 4, which comprises the following steps:
(1) Mixing nano silicon nitride with a coupling agent and acetone, and performing modification treatment to obtain modified nano silicon nitride;
(2) Mixing the modified nano silicon nitride obtained in the step (1) with a styrene-ethylene butene polymer, chlorinated butyl rubber, calcium sulfate whisker, graphene oxide, stearic acid, nano zinc oxide, carbon black and a negative ion additive, and mixing to obtain a premix;
(3) Mixing the premix obtained in the step (2) with an anti-aging agent, a vulcanization accelerator and sulfur, and pressing after open milling to obtain a sheet;
(4) And (3) vulcanizing the sheet obtained in the step (3) to obtain the wear-resistant antibacterial shoe material.
6. The method according to claim 5, wherein the vulcanizing temperature in the step (4) is 120-140 ℃ and the vulcanizing pressure is 10-15 mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111159771.1A CN113698710B (en) | 2021-09-30 | 2021-09-30 | Wear-resistant antibacterial shoe material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111159771.1A CN113698710B (en) | 2021-09-30 | 2021-09-30 | Wear-resistant antibacterial shoe material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113698710A CN113698710A (en) | 2021-11-26 |
| CN113698710B true CN113698710B (en) | 2023-08-25 |
Family
ID=78662417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111159771.1A Active CN113698710B (en) | 2021-09-30 | 2021-09-30 | Wear-resistant antibacterial shoe material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113698710B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115506157B (en) * | 2022-10-19 | 2024-02-13 | 卡尔美体育用品有限公司 | Antibacterial warm down jacket fabric and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2452910A1 (en) * | 2003-12-12 | 2005-06-12 | Bayer Inc. | Butyl rubber composition for tire treads |
| CN104497453A (en) * | 2014-11-26 | 2015-04-08 | 上海品科橡塑材料有限公司 | New rubber wear-resisting agent and composition thereof |
| CN107973945A (en) * | 2017-12-19 | 2018-05-01 | 中央军委后勤保障部军需装备研究所 | A kind of wear-resisting anti-wet and slippery rubber sole formula and preparation method thereof |
| CN109824966A (en) * | 2018-12-10 | 2019-05-31 | 华南理工大学 | A kind of wear-resistance and oil-resistance engineering sole material and preparation method thereof |
| CN111410799A (en) * | 2020-03-13 | 2020-07-14 | 泉州市华创园智能研究有限公司 | Anti-slip wear-resistant shoe material and preparation method thereof |
| CN111808417A (en) * | 2020-07-06 | 2020-10-23 | 浙江森马服饰股份有限公司 | PU (polyurethane) foaming shoe material capable of releasing negative ions and preparation method thereof |
-
2021
- 2021-09-30 CN CN202111159771.1A patent/CN113698710B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2452910A1 (en) * | 2003-12-12 | 2005-06-12 | Bayer Inc. | Butyl rubber composition for tire treads |
| CN104497453A (en) * | 2014-11-26 | 2015-04-08 | 上海品科橡塑材料有限公司 | New rubber wear-resisting agent and composition thereof |
| CN107973945A (en) * | 2017-12-19 | 2018-05-01 | 中央军委后勤保障部军需装备研究所 | A kind of wear-resisting anti-wet and slippery rubber sole formula and preparation method thereof |
| CN109824966A (en) * | 2018-12-10 | 2019-05-31 | 华南理工大学 | A kind of wear-resistance and oil-resistance engineering sole material and preparation method thereof |
| CN111410799A (en) * | 2020-03-13 | 2020-07-14 | 泉州市华创园智能研究有限公司 | Anti-slip wear-resistant shoe material and preparation method thereof |
| CN111808417A (en) * | 2020-07-06 | 2020-10-23 | 浙江森马服饰股份有限公司 | PU (polyurethane) foaming shoe material capable of releasing negative ions and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113698710A (en) | 2021-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107216504B (en) | A kind of high abrasion rare-earth rubber material for shoes and preparation method thereof | |
| EP2098540B1 (en) | Method for producing modified conjugated diene polymer, modified conjugated diene polymer, and rubber composition | |
| JP5147788B2 (en) | Method for producing rubber composition, rubber composition obtained thereby, and tire using the rubber composition | |
| JP5614308B2 (en) | Method for producing rubber composition for tire | |
| CN108192162B (en) | A kind of Sports shoe sole abrasive rubber and preparation method thereof | |
| CN113698710B (en) | Wear-resistant antibacterial shoe material and preparation method thereof | |
| JP5873063B2 (en) | Rubber composition for anti-vibration rubber and anti-vibration rubber | |
| WO2016199915A1 (en) | Rubber composition and pneumatic tire using same | |
| CN108530764A (en) | A kind of thermoplastic elastomer (TPE) of halogen-free flame-retardant and preparation method thereof | |
| JP2019001978A (en) | Compound for producing elastic composite material, product including the same, and tread rubber | |
| KR101305441B1 (en) | Method for manufacturing of Starch/rubber Latex Compound Using Coupling reagent | |
| KR20110087468A (en) | Tire tread rubber composition having improved fuel efficiency and static dissipative and tire using the same | |
| KR20180038146A (en) | Rubber composition and tire comprising the same | |
| JP6234172B2 (en) | Rubber composition for anti-vibration rubber and anti-vibration rubber | |
| JP2007031587A (en) | Rubber composition for tire | |
| JPH0229097B2 (en) | ||
| JP2007099896A (en) | Rubber composition | |
| CN112239572B (en) | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof | |
| WO2020218358A1 (en) | Rubber composition, crosslinked rubber product obtained from said rubber composition, and method for producing said rubber composition | |
| CN113444300B (en) | Rubber composition for sole material, vulcanized rubber, and preparation method and application thereof | |
| CN115636991B (en) | High-strength scorch-resistant chloroprene rubber | |
| Dutta et al. | Utilization of modified soybean oil in passenger car radial tyre tread and sidewall compound to promote green mobility | |
| CN111732765B (en) | High-elongation-at-break diene rubber compound and preparation method thereof | |
| KR101247392B1 (en) | A rubber composite | |
| JP2019026757A (en) | Rubber composition for tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |