CN113980414B - Folding-resistant anti-aging sole material and folding-resistant anti-aging sole material - Google Patents
Folding-resistant anti-aging sole material and folding-resistant anti-aging sole material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- 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
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a folding-resistant anti-aging sole material which comprises the following components in parts by mass: 50-100 parts of SBS, 30-50 parts of natural rubber, 3-8 parts of antibacterial agent, 20-50 parts of softening oil, 10-15 parts of inorganic filler, 2-8 parts of coupling agent, 2-3 parts of vulcanizing agent, 3-5 parts of vulcanization accelerator, 2-6 parts of diethylenetriamine and 2-6 parts of tannin. The sole material has good ultraviolet aging resistance and folding resistance, and also has good antibacterial effect, and can prevent foot odor phenomenon generated after a user wears the shoe to exercise.
Description
Technical Field
The invention relates to the technical field of sole processing, in particular to a folding-resistant anti-aging sole material.
Background
The styrene-butadiene-styrene triblock thermoplastic elastomer (SBS) is a thermoplastic elastomer with wide application, has lower price compared with other thermoplastic elastomer materials, stable product supply, better physical and mechanical properties, good wear resistance and excellent processability, and is a polymer material with wide application and excellent performance. Compared with the traditional rubber material processing process, the method reduces the vulcanization process, simplifies the production flow, improves the environment of a production workshop, reduces the investment of factories on equipment and land, reduces the production cost, simultaneously recycles the leftover materials in production according to a certain proportion, is beneficial to reducing the discharge of solid wastes and protecting the environment, and is widely used as sole materials in the shoe industry.
The SBS has the advantages that: 1. the special structural performance characteristics of the anti-skid and rebound performances are good; 2. the original color difference of the manufactured sole is small; 3. the sole prepared by the SBS mixed formula has small compression deformation degree and high upper foot comfort level. The appearance of SBS is a white or gold porous round bar or pellet master. The molecular weight of linear SBS is generally 80-120,000, the molecular weight of radial SBS is generally 140-300,000, and the relative density is 0.92-0.95. The main chain of SBS has good tensile property, elasticity, small permanent deformation, excellent deflection resistance, rebound resilience, larger friction coefficient and excellent plastic processing property, but because of a large number of unsaturated double bonds in the main chain, SBS is not oxidation-resistant, and an antioxidant and an ultraviolet absorber are often added in the use of easy color change under ultraviolet irradiation to shield ultraviolet damage, so that the purpose of prolonging the service life of SBS products is achieved. However, most shoes manufactured by SBS thermoplastic elastomer in the market at present have poor weather resistance and wear resistance, and are easy to wear and generate sole deformation.
The SBS is modified mainly into two types of chemical modification and blending modification, and aims to improve the performance of the existing SBS, wherein the SBS triblock copolymer is provided with a polystyrene block and a polybutadiene block, the polystyrene block is used as a physical crosslinking point, the PS block is in a glass state at normal temperature, the solubility and the thermoplasticity are given to the PS block, the PB is given to the softness and the rebound resilience of the PS block, and the characteristics of the PS block and the PB are combined, so that the SBS has the elasticity similar to vulcanized rubber, and the polystyrene block is in a viscous state at high temperature, and the physical crosslinking point is destroyed, so that the SBS can be plasticized and molded. Since SBS is a nonpolar material, the application in polar material bonding is limited.
Titanium dioxide, the whitest material in the world, titanium dioxide (TiO 2 ) Is a wide band gap transparent metal oxide semiconductor, and three common crystal structures are provided: rutile, anatase and brookite, which are common in nature are anatase phase and rutile phase, have optical band gaps above 3.0eV, and have excellent photoinduced super-hydrophilicity, photocatalytic property and anti-agingPhoto-corrosiveness, antibacterial property, etc. Titanium dioxide is often used as an ultraviolet absorber in various materials, and titanium dioxide is absorbed in UVA and UVB wave bands, and can scatter ultraviolet rays to a certain extent besides absorbing ultraviolet rays, but the nano titanium dioxide has high surface energy, is easy to agglomerate, and has the problems of difficult dispersion in a matrix and the like.
Patent CN 104804358A discloses a lightweight and aging-resistant thermoplastic sole and a preparation method thereof, the lightweight and aging-resistant thermoplastic sole is composed of the following components: styrene-butadiene-styrene block copolymer (SBS), polyolefin block copolymer, ethylene-vinyl acetate copolymer, white mineral oil, antioxidant, foaming agent, zinc stearate, wear-resisting agent and inorganic filler, mixing the above components at high speed, premixing for 4-7 minutes, and then passing the premix through a double screw extruder. The sole prepared by the invention has better weather resistance, but does not solve the problem of foot odor after sports sweats.
At present, the comfort of the sole material in the prior art is considered more, and the folding endurance of the sole is often neglected. In the environments of construction sites, workshops, factories and the like, the sole material is required to have certain folding resistance, and particularly in the use environment of easily cutting the sole, the requirement on the folding resistance of the sole material is higher.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a folding-resistant anti-aging sole, which has a good anti-ultraviolet aging effect and folding-resistant antibacterial effect, and can prevent the foot odor of a user after putting on the sole.
In order to achieve the aim, the invention provides a folding-resistant anti-aging sole material which has better ultraviolet aging resistance, folding resistance, bacteriostasis and wear resistance.
The specific technical scheme is as follows:
a folding-resistant anti-aging sole material comprises the following components in parts by weight: 50-100 parts of SBS, 30-50 parts of natural rubber, 3-8 parts of antibacterial agent, 20-50 parts of softening oil, 10-15 parts of inorganic filler, 2-8 parts of coupling agent, 2-3 parts of vulcanizing agent, 3-5 parts of vulcanization accelerator, 2-6 parts of diethylenetriamine and 2-6 parts of tannin.
Because SBS is a nonpolar substance, the invention adopts the natural rubber which is also nonpolar to blend with SBS to enhance the compatibility of the blend and improve the mechanical property of the blend; the nanometer titanium dioxide is subjected to illumination, electrons on titanium atoms are excited by light, and the running orbit is changed, so that extremely strong oxidizing capacity is generated, free radicals and active cations are released, cells are decomposed, proteins are mutated, and an antibacterial effect is achieved; the nano titanium dioxide is coated with the silicon dioxide and the aluminum oxide with the reinforcing function for modification, so that the whiteness of the nano titanium dioxide is improved, and the surface of the nano titanium dioxide is coated with compact SiO (silicon dioxide) under the condition that the ultraviolet absorption capacity of the nano titanium dioxide is not influenced 2 And Al 2 O 3 The Ti-O-Si bond is formed on the interface between the silicon dioxide coating layer and the nanoscale titanium dioxide particles in a chemical bonding mode, the energy band gap is increased, the photocatalytic activity of the nanoscale titanium dioxide is improved, and the thermal stability of the nanoscale titanium dioxide is effectively improved, so that the problem that the utilization rate of the nanoscale titanium dioxide to visible light is low is solved; then carrying out organic surface treatment on the titanium dioxide powder to form an organic protective layer, so that the weather resistance and the dispersibility of the nano titanium dioxide powder are obviously improved; the chlorhexidine gluconate and the nano titanium dioxide produce a synergistic effect, so that the antibacterial effect of the material can be enhanced.
The SBS is the mixture of star SBS and linear SBS with the mass ratio of 1-2:2-3, the brand of the star SBS is 1475, and the brand of the linear SBS is 1401; the SBS of different brands has larger difference in tensile strength and breaking elongation due to the difference of S/B ratio and molecular shape in the molecule, wherein the linear SBS has higher tensile strength but lower breaking elongation, and the star SBS has lower tensile strength but higher breaking elongation, and the advantages and disadvantages of the linear SBS and the star SBS can be complemented by controlling the ratio of the linear SBS and the star SBS, so that the wear resistance of the sole can be increased under the action of ensuring certain mechanical strength.
The antibacterial agent is one or two or more of nano titanium dioxide, modified nano titanium dioxide and chlorhexidine gluconate; preferably, the antibacterial agent is a mixture of nano titanium dioxide and chlorhexidine gluconate; more preferably, the antibacterial agent is a mixture of modified nano titanium dioxide and chlorhexidine gluconate with a mass ratio of 1-2:1-2.
The preparation method of the modified nano titanium dioxide comprises the following steps:
1) Adding 10-15g of titanium dioxide into 30-40mL of water and 20-30mL of propylene glycol, regulating the pH value of the solution to 9-10 by using 0.5-1mol/L NaOH aqueous solution, heating to 50-70 ℃, and stirring to obtain titanium dioxide slurry;
2) Adding 0.1-0.2g of silicon dioxide powder into the titanium dioxide slurry prepared in the step 1), stirring for 30-60min, adding 0.3-0.5g of aluminum oxide powder, continuously stirring for 30-60min, adding 0.1-2g of triethoxy octyl silane, stirring for 10-60min, filtering, washing a filter cake with water, drying at 60-80 ℃ for 20-24h, and grinding to obtain modified titanium dioxide.
Because the nano titanium dioxide has high surface energy, is easy to agglomerate in the blending matrix, and takes the enhancement of the mechanical property of the matrix into consideration, the nano titanium dioxide is coated with silicon dioxide and aluminum oxide with reinforcing function, and the ultraviolet absorption function is not influenced. The surface of the modified nano titanium dioxide is coated with compact SiO 2 And Al 2 O 3 The Ti-O-Si bond is formed on the interface between the coating layer and the nanoscale titanium dioxide particles in a chemical bonding mode, the energy band gap is increased, the photocatalytic activity of the nanoscale titanium dioxide is improved, the thermal stability of the nanoscale titanium dioxide is effectively improved, the particle size of the coated nanoscale titanium dioxide is reduced, the particle size distribution is uniform, the surface is smooth, and then the coated nanoscale titanium dioxide is subjected to organic surface treatment to form an organic protective layer, so that the weather resistance and the dispersibility of the nanoscale titanium dioxide are obviously improved.
Chlorhexidine gluconate itself has a positive charge and is a bacteriostatic agent with broad-spectrum antimicrobial activity. The inventor discovers that chlorhexidine gluconate and nano titanium dioxide are compounded into the folding-resistant anti-aging sole material, and the folding-resistant anti-aging sole material canSo as to obviously enhance the antibacterial effect of the material, in particular to the antibacterial effect of the Epidermophyton floccosum. The reason for this may be that the modified titanium dioxide surface is coated with SiO 2 And Al 2 O 3 The chlorhexidine gluconate with positive charges can be adsorbed on the surface of nano titanium dioxide due to electrostatic interaction, and through synergistic effect, phosphate groups with negative charges on the surface of bacteria can be adsorbed, so that the phosphate groups gradually permeate into lipid layers and protein layers of cell plasma, the permeability of cell membranes is changed, the cell contents are extravasated, and the death of microorganisms is caused, so that the antibacterial effect is achieved.
The softening oil is naphthenic white oil.
The inorganic filler is nano silicon dioxide and nano CaCO 3 One or two or more of montmorillonite and kaolin; the preferred inorganic filler is nano silica; the more preferred inorganic filler is modified nano-silica, which is prepared by the following steps: 1-2g of aminosilane coupling agent is weighed and added into 40-50g of absolute ethyl alcohol, the pH value of the solution is regulated to 3-4 by 30wt% of acetic acid aqueous solution, 3-6g of nano silicon dioxide is added after the solution is stirred to be completely dissolved, the mixture is stirred for 3-5 hours at 60-80 ℃, the mixture is cooled to 20-40 ℃, centrifuged, sediment is collected, and the sediment is dried for 10-12 hours at 100-120 ℃ to obtain the modified nano silicon dioxide.
The coupling agent is one of silicon-69 and silicon-75.
The vulcanizing agent is elemental sulfur.
The vulcanization accelerator is one of zinc oxide and stearic acid.
Compared with the prior art, the invention has the beneficial effects that:
1. the nonpolar natural rubber and SBS are used for blending, so that the compatibility of the nonpolar natural rubber and SBS is improved, and the mechanical property of the material is enhanced;
2. the advantages and disadvantages of the linear SBS and the star SBS can be complemented by mixing the star SBS and the linear SBS, and the wear resistance of the sole can be increased under the effect of ensuring certain mechanical strength;
3. by modifying the nano titanium dioxide, the inorganic protective layer and the organic protective layer are coated on the surface of the titanium dioxide, so that the photocatalysis capability and the service life of the nano titanium dioxide can be improved, the compatibility between the nano titanium dioxide and other materials can be enhanced, and the nano titanium dioxide can be better dispersed in the materials.
4. Through the compounding of the modified nano titanium dioxide and the chlorhexidine gluconate, the chlorhexidine gluconate is adsorbed on the surface of the nano titanium dioxide through static electricity, and the antibacterial effect of the material can be enhanced through synergistic effect.
5. The addition of diethylenetriamine and tannin can effectively improve the dispersibility of inorganic filler-titanium dioxide and silicon dioxide, promote the formation of a complex network structure and solve the problem of reduced folding resistance caused by the addition of the inorganic filler.
Detailed Description
The invention will be described in further detail with reference to specific examples. The procedures, conditions, experimental methods, etc. for carrying out the present invention are common general knowledge and knowledge in the art, except for the following specific references, and the present invention is not particularly limited.
The sources of some of the raw materials in the examples of the present invention are as follows, and the raw materials used in the examples are all available from conventional commercial sources or can be prepared by conventional methods unless specifically indicated otherwise:
SBS1475, star, S/B40/60, purchased from Star Huiz Li Changrong rubber Co.
SBS1401, linear, 40/60S/B purchased from Basil petrochemicals division, china.
Natural rubber purchased from the company of MaoMin City, inc. of MaoDi petrochemical Co., ltd, had a total solids content of 61.77% and a dry rubber content of 61.19%.
Nanometer titanium dioxide is purchased from Hubei British chemical New material Co., ltd, the crystal form is rutile, the content is 99.8%, the CAS number is 23-556-4, and the model is CR828.
Cycloalkyl white oil, purchased from Hebei Jiale Petroleum technologies Co., ltd, is colorless transparent or yellowish white liquid, has an acid value of <0.15mgKOH/g, a saturated hydrocarbon content of 87.55% -93.86%, and an aromatic hydrocarbon content of 6.14% -11.96%.
Nano silicon dioxide, purchased from Shanghai super Wei nanotechnology Co., ltd., model CW-SiO 2 -001, average particle diameter of 20nm, purity of 99.9%, specific surface area of 80m 2 Per gram, bulk density of 0.23g/cm 3 。
Chlorhexidine gluconate purchased from Ji nan Wan De Feng environmental protection technology Co., ltd, CAS number 18372-51-0, content 99.9%, model number of food grade.
Silicon-69, purchased from Jinan Huijun chemical industry Co., ltd, with a content of 99%, and a light yellow transparent liquid, model si-69.
Elemental sulfur purchased from Shanghai Shaoshi nanotechnology Co., ltd., pale yellow powder in appearance and a density of 2g/cm 3 The melting point was 119 ℃.
Zinc oxide, commercially available from Shanghai Chaowei nanotechnology Co., ltd., model CW-ZnO-002, average particle diameter of 200nm, purity of 99.9%, specific surface area of 19m 2 Per gram, bulk density of 1.3g/cm 3 。
Coli, purchased from the China center for Industrial microorganism culture Collection, with a strain accession number of CICC 10003.
Epidermophyton floccosum purchased from Shanghai Africa Biotech Inc., purity 100%, specification of lyophilization tube, and product number of XY-WSW-1200.
Example 1
A preparation method of a folding-resistant anti-aging sole material comprises the following steps:
s1, mixing materials: weighing 100g of SBS, 50g of natural rubber, 8g of nano titanium dioxide, 30g of cycloalkyl white oil, 15g of modified nano silicon dioxide and 8g of silicon-69 according to a formula, and banburying in an internal mixer to obtain master batch; the mixing time is 150s, and the banburying temperature is 130 ℃; the SBS is a mixture of star-shaped SBS and linear SBS with the mass ratio of 1:2;
s2, tabletting the masterbatch: placing the masterbatch on a two-roll cooling open mill, adding 3g of elemental sulfur and 5g of zinc oxide after the sizing material is wrapped on a roll, then respectively carrying out rubber 3 times at the left and right 3/4 of the roll, then carrying out thin pass for 5 times, and pressing into a film with 110 multiplied by 3 mm;
s3, vulcanization molding: adding the rubber sheet into an extruder in a cold feeding mode, extruding and injecting the rubber sheet into a sole die cavity, and performing compression molding vulcanization molding to obtain a folding-resistant anti-aging sole material; the extrusion temperature is 140 ℃, the vulcanization temperature of the sole die cavity is 150 ℃, and the vulcanization time is 10min.
The preparation method of the modified nano silicon dioxide comprises the following steps: 2g of aminosilane coupling agent is weighed and added into 50g of absolute ethyl alcohol, the pH value of the solution is regulated to 4 by 30wt% of acetic acid aqueous solution, 6g of nano silicon dioxide is added after the solution is stirred to be completely dissolved, the mixture is stirred for 4 hours at 80 ℃, the mixture is cooled to 30 ℃, centrifuged, the precipitate is collected, and the precipitate is dried for 12 hours at 120 ℃ to obtain the modified nano silicon dioxide.
Example 2
A preparation method of a folding-resistant anti-aging sole material comprises the following steps:
s1, mixing materials: weighing 100g of SBS, 50g of natural rubber, 8g of chlorhexidine gluconate, 30g of cycloalkyl white oil, 15g of modified nano silicon dioxide and 8g of silicon-69 according to a formula, and banburying in an internal mixer to obtain master batch; the mixing time is 150s, and the banburying temperature is 130 ℃; the SBS is a mixture of star-shaped SBS and linear SBS with the mass ratio of 1:2;
s2, tabletting the masterbatch: placing the masterbatch on a two-roll cooling open mill, adding 3g of elemental sulfur and 5g of zinc oxide after the sizing material is wrapped on a roll, then respectively carrying out rubber 3 times at the left and right 3/4 of the roll, then carrying out thin pass for 5 times, and pressing into a film with 110 multiplied by 3 mm;
s3, vulcanization molding: adding the rubber sheet into an extruder in a cold feeding mode, extruding and injecting the rubber sheet into a sole die cavity, and performing compression molding vulcanization molding to obtain a folding-resistant anti-aging sole material; the extrusion temperature is 140 ℃, the vulcanization temperature of the sole die cavity is 150 ℃, and the vulcanization time is 10min.
The preparation method of the modified nano silicon dioxide comprises the following steps: 2g of aminosilane coupling agent is weighed and added into 50g of absolute ethyl alcohol, the pH value of the solution is regulated to 4 by 30wt% of acetic acid aqueous solution, 6g of nano silicon dioxide is added after the solution is stirred to be completely dissolved, the mixture is stirred for 4 hours at 80 ℃, the mixture is cooled to 30 ℃, centrifuged, the precipitate is collected, and the precipitate is dried for 12 hours at 120 ℃ to obtain the modified nano silicon dioxide.
Example 3
A preparation method of a folding-resistant anti-aging sole material comprises the following steps:
s1, mixing materials: weighing 100g of SBS, 50g of natural rubber, 8g of modified nano titanium dioxide, 30g of cycloalkyl white oil, 15g of modified nano silicon dioxide and 8g of silicon-69 according to a formula, and banburying in an internal mixer to obtain master batch; the mixing time is 150s, and the banburying temperature is 130 ℃; the SBS is a mixture of star-shaped SBS and linear SBS with the mass ratio of 1:2;
s2, tabletting the masterbatch: placing the masterbatch on a two-roll cooling open mill, adding 3g of elemental sulfur and 5g of zinc oxide after the sizing material is wrapped on a roll, then respectively carrying out rubber 3 times at the left and right 3/4 of the roll, then carrying out thin pass for 5 times, and pressing into a film with 110 multiplied by 3 mm;
s3, vulcanization molding: adding the rubber sheet into an extruder in a cold feeding mode, extruding and injecting the rubber sheet into a sole die cavity, and performing compression molding vulcanization molding to obtain a folding-resistant anti-aging sole material; the extrusion temperature is 140 ℃, the vulcanization temperature of the sole die cavity is 150 ℃, and the vulcanization time is 10min.
The preparation method of the modified nano titanium dioxide comprises the following steps:
1) Adding 10g of titanium dioxide into 40mL of water and 20-30mL of propylene glycol solution, adjusting the pH value of the solution to 10 by using 1mol/L NaOH aqueous solution, heating to 60 ℃, and stirring to obtain titanium dioxide slurry;
2) Adding 0.2g of silicon dioxide powder into the titanium dioxide slurry prepared in the step 1), stirring for 60min, adding 0.5g of aluminum oxide powder, continuously stirring for 60min, adding 1g of triethoxy octyl silane, stirring for 30min, filtering, washing a filter cake with water, drying at 80 ℃ for 24h, and grinding to obtain modified titanium dioxide.
The preparation method of the modified nano silicon dioxide comprises the following steps: 2g of aminosilane coupling agent is weighed and added into 50g of absolute ethyl alcohol, the pH value of the solution is regulated to 4 by 30wt% of acetic acid aqueous solution, 6g of nano silicon dioxide is added after the solution is stirred to be completely dissolved, the mixture is stirred for 4 hours at 80 ℃, the mixture is cooled to 30 ℃, centrifuged, the precipitate is collected, and the precipitate is dried for 12 hours at 120 ℃ to obtain the modified nano silicon dioxide.
Example 4
A preparation method of a folding-resistant anti-aging sole material comprises the following steps:
s1, mixing materials: weighing 100g of SBS, 50g of natural rubber, 8g of antibacterial agent, 30g of cycloalkyl white oil, 15g of modified nano silicon dioxide and 8g of silicon-69 according to a formula, and banburying in an internal mixer to obtain master batch; the mixing time is 150s, and the banburying temperature is 130 ℃; the SBS is a mixture of star-shaped SBS and linear SBS with the mass ratio of 1:2; the antibacterial agent is a mixture of modified nano titanium dioxide and chlorhexidine gluconate with a mass ratio of 2:1;
s2, tabletting the masterbatch: placing the masterbatch on a two-roll cooling open mill, adding 3g of elemental sulfur and 5g of zinc oxide after the sizing material is wrapped on a roll, then respectively carrying out rubber 3 times at the left and right 3/4 of the roll, then carrying out thin pass for 5 times, and pressing into a film with 110 multiplied by 3 mm;
s3, vulcanization molding: adding the rubber sheet into an extruder in a cold feeding mode, extruding and injecting the rubber sheet into a sole die cavity, and performing compression molding vulcanization molding to obtain a folding-resistant anti-aging sole material; the extrusion temperature is 140 ℃, the vulcanization temperature of the sole die cavity is 150 ℃, and the vulcanization time is 10min.
The preparation method of the modified nano titanium dioxide comprises the following steps:
1) Adding 10g of titanium dioxide into 40mL of water and 20-30mL of propylene glycol solution, adjusting the pH value of the solution to 10 by using 1mol/L NaOH aqueous solution, heating to 60 ℃, and stirring to obtain titanium dioxide slurry;
2) Adding 0.2g of silicon dioxide powder into the titanium dioxide slurry prepared in the step 1), stirring for 60min, adding 0.5g of aluminum oxide powder, continuously stirring for 60min, adding 1g of triethoxy octyl silane, stirring for 30min, filtering, washing a filter cake with water, drying at 80 ℃ for 24h, and grinding to obtain modified titanium dioxide.
The preparation method of the modified nano silicon dioxide comprises the following steps: 2g of aminosilane coupling agent is weighed and added into 50g of absolute ethyl alcohol, the pH value of the solution is regulated to 4 by 30wt% of acetic acid aqueous solution, 6g of nano silicon dioxide is added after the solution is stirred to be completely dissolved, the mixture is stirred for 4 hours at 80 ℃, the mixture is cooled to 30 ℃, centrifuged, the precipitate is collected, and the precipitate is dried for 12 hours at 120 ℃ to obtain the modified nano silicon dioxide.
Example 5
A preparation method of a folding-resistant anti-aging sole material comprises the following steps:
s1, mixing materials: weighing 100g of SBS, 50g of natural rubber, 8g of antibacterial agent, 30g of cycloalkyl white oil, 15g of modified nano silicon dioxide, 8g of silicon-69, 5g of diethylenetriamine and 3g of tannin according to a formula, and banburying in an internal mixer to obtain master batch; the mixing time is 150s, and the banburying temperature is 130 ℃; the SBS is a mixture of star-shaped SBS and linear SBS with the mass ratio of 1:2; the antibacterial agent is a mixture of modified nano titanium dioxide and chlorhexidine gluconate with a mass ratio of 2:1;
s2, tabletting the masterbatch: placing the masterbatch on a two-roll cooling open mill, adding 3g of elemental sulfur and 5g of zinc oxide after the sizing material is wrapped on a roll, then respectively carrying out rubber 3 times at the left and right 3/4 of the roll, then carrying out thin pass for 5 times, and pressing into a film with 110 multiplied by 3 mm;
s3, vulcanization molding: adding the rubber sheet into an extruder in a cold feeding mode, extruding and injecting the rubber sheet into a sole die cavity, and performing compression molding vulcanization molding to obtain a folding-resistant anti-aging sole material; the extrusion temperature is 140 ℃, the vulcanization temperature of the sole die cavity is 150 ℃, and the vulcanization time is 10min.
The preparation method of the modified nano titanium dioxide is the same as that of the embodiment 4, and is not repeated here.
The preparation method of the modified nano-silica is the same as that of example 4, and is not repeated here.
Test case
And (3) ageing resistance test:
the folding-resistant anti-aging sole materials prepared in comparative examples and examples 1-4 are placed in an ultraviolet light accelerated aging test box, the ultraviolet light accelerated aging test box is irradiated for 10 days and 20 days respectively at the wavelength of 340nm, then the ultraviolet light accelerated aging test box is sampled, each performance characterization is carried out after 24 hours, the samples with different treatment times are tested for tensile strength and elongation at break, each group of samples are tested for 3 times, the test results are averaged, and the test results are shown in Table 2.
The sole subjected to the aging resistance test is subjected to tensile property test, and according to GB/T1040.1-2006, determination of Plastic tensile Property part 1: general rule, cutting samples into dumbbell-shaped sample bars with the length of 115mm, the width of 10mm and the thickness of 4mm, carrying out a tensile test on a universal tester, wherein the tensile rate is 50mm/min, the clamp spacing is 115mm, measuring the tensile strength of the samples, measuring 3 times of each group of samples, taking an average value of the test results, and the test results are shown in table 1:
table 1: anti-aging performance test of folding-resistant anti-aging sole material
The smaller the ultraviolet ageing color difference and the ultraviolet ageing yellow index value, the stronger the ultraviolet ageing resistance of the material, the tensile strength is related to the ultraviolet ageing degree, and the higher the ageing degree is, the weaker the tensile strength of the material is. As can be seen from the data in Table 2, the folding-resistant anti-aging sole material prepared in example 3 has the best ultraviolet aging resistance, while example 3 is different from other examples in that modified titanium dioxide and chlorhexidine gluconate are added, probably because the surface of the modified titanium dioxide is coated with dense SiO 2 And Al 2 O 3 The Ti-O-Si bond is formed on the interface between the coating layer and the nanoscale titanium dioxide particles in a chemical bonding mode, the energy band gap is increased, the photocatalytic activity of the nanoscale titanium dioxide is improved, the thermal stability of the nanoscale titanium dioxide is effectively improved, the particle size of the coated nanoscale titanium dioxide is reduced, the particle size distribution is uniform, the surface is smooth, and the coated nanoscale titanium dioxide is subjected to organic surface treatment to form an organic protective layer, so that the long-acting ultraviolet light absorption effect can be kept, the degradation effect of light on the sole is reduced, and the service life of the sole is prolonged.
Antibacterial performance test: taking escherichia coli ATCC8099 and staphylococcus aureus ATCC6538 as examples, the antibacterial rate is the maximum percentage of bacteria that are inhibited and killed under certain antibacterial agent content and experimental conditions. The resistances prepared in examples 1 to 4 were brought to a temperature of 37 ℃The folded anti-aging sole material is placed in a special plastic bag corresponding to 10cm 2 2mL of inoculation bacteria liquid is added, air which is equivalent to the inoculation bacteria liquid is introduced into a plastic bag, the plastic bag is heat-sealed, the plastic bag is oscillated for 24 hours at 37+/-1 ℃, the viable bacteria number is measured by a dilution plate culture method, the antibacterial rate is calculated, and the specific test results are shown in Table 2:
table 2: antibacterial rate test result (%)
| Coli bacterium | Epidermophyton floccosum | |
| Example 1 | 90.1 | 88.3 |
| Example 2 | 92.6 | 90.2 |
| Example 3 | 99.5 | 92.5 |
| Example 4 | 100 | 95.3 |
As can be seen from the data in Table 2, the folding-resistant anti-aging sole material prepared by the inventionHas good antibacterial effect, and is remarkable in that the sole has good inhibiting effect on epidermophyton floccosum causing beriberi, probably due to SiO coated on the modified titanium dioxide surface 2 And Al 2 O 3 The chlorhexidine gluconate with positive charges can be adsorbed on the surface of nano titanium dioxide due to electrostatic interaction, and can adsorb phosphate groups with negative charges on the surface of bacteria, so that the phosphate groups gradually permeate into lipid layers and protein layers of cytoplasm, thereby changing the permeability of cell membranes, enabling cell contents to permeate outwards, leading to death of microorganisms, and the synergistic effect of the two can enhance the antibacterial effect of the product.
Abrasion resistance test: the folding-resistant anti-aging sole materials prepared in examples 1-4 were subjected to abrasion resistance testing according to GB/T1689-2014 test for abrasion resistance of vulcanized rubber (with an Aldrich abrasion tester), each group of samples were tested 3 times, the test results were averaged, and specific test results are shown in Table 3:
table 3: abrasion resistance test result of folding-resistant anti-aging sole material
| Wearing quality (g) | |
| Example 1 | 0.98 |
| Example 2 | 1.34 |
| Example 3 | 0.58 |
| Example 4 | 0.35 |
The smaller the abrasion quality, the better the abrasion resistance of the material is, and the experimental result in table 3 shows that the abrasion resistance of the material can be obviously improved by adding the modified nano titanium dioxide, and the possible reason is that after inorganic coating and organic modification are carried out on the reinforced silicon dioxide and aluminum oxide for the nano titanium dioxide, the dispersibility and mechanical property of the nano titanium dioxide in the matrix are obviously improved, thereby improving the abrasion resistance of the matrix.
Folding endurance test:
the test is carried out by referring to the method specified in GB/T3903.1-2017 whole shoe test method folding endurance.
Sample size: 200mm 50mm 20mm
Test conditions:
qu Naojiao degrees: 50 degree
Flexural frequency: 230 times/min
Number of flexing: 4 ten thousand times
Length of cut: 5mm of
Table 4: folding-resistant and aging-resistant sole material folding-resistant test result
| Crack length mm | |
| Example 4 | 9.8 |
| Example 5 | 6.4 |
As can be seen from the above table, the folding endurance and aging resistance of the folding endurance and aging resistance sole material of example 5 of the present invention is significantly better than that of the folding endurance and aging resistance sole material of example 4. The reasons for this may be: the diethylenetriamine and tannin are added into the sole material, so that the dispersibility of inorganic filler-titanium dioxide and silicon dioxide can be effectively improved, a complex network structure can be formed, and the problem of reduced folding resistance caused by the addition of the inorganic filler can be solved.
Claims (7)
1. The folding-resistant anti-aging sole material is characterized by comprising the following components in parts by weight: 50-100 parts of SBS, 30-50 parts of natural rubber, 3-8 parts of antibacterial agent, 20-50 parts of softening oil, 10-15 parts of inorganic filler, 2-8 parts of coupling agent, 2-3 parts of vulcanizing agent, 3-5 parts of vulcanization accelerator, 2-6 parts of diethylenetriamine and 2-6 parts of tannin; the antibacterial agent is a mixture of modified nano titanium dioxide and chlorhexidine gluconate with the mass ratio of 1-2:1-2;
the preparation method of the modified nano titanium dioxide comprises the following steps:
1) Adding 10-15g of titanium dioxide into 30-40mL of water and 20-30mL of propylene glycol, regulating the pH value of the solution to 9-10 by using 0.5-1mol/L NaOH aqueous solution, heating to 50-70 ℃, and stirring to obtain titanium dioxide slurry;
2) Adding 0.1-0.2g of silicon dioxide powder into the titanium dioxide slurry prepared in the step 1), stirring for 30-60min, adding 0.3-0.5g of aluminum oxide powder, continuously stirring for 30-60min, adding 0.1-2g of triethoxy octyl silane, stirring for 10-60min, filtering, washing a filter cake with water, drying at 60-80 ℃ for 20-24h, and grinding to obtain modified titanium dioxide.
2. The fold-resistant anti-aging sole material of claim 1, wherein: the SBS is the mixture of the star SBS and the linear SBS with the mass ratio of 1-2:2-3.
3. The fold-resistant anti-aging sole material of claim 1, wherein the softening oil is a naphthenic white oil.
4. The fold-resistant anti-aging sole material of claim 1, wherein: the inorganic filler is one or two or more of nano silicon dioxide, nano CaCO3, montmorillonite and kaolin.
5. The fold-resistant anti-aging sole material of claim 1, wherein: the inorganic filler is modified nano silicon dioxide; the preparation method of the modified nano silicon dioxide comprises the following steps: 1-2g of aminosilane coupling agent is weighed and added into 40-50g of absolute ethyl alcohol, the pH value of the solution is regulated to 3-4 by using 20-30wt% of acetic acid aqueous solution, 3-6g of nano silicon dioxide is added after the solution is stirred to be completely dissolved, the mixture is stirred for 3-5 hours at 60-80 ℃, the mixture is cooled to 20-40 ℃, centrifuged, the precipitate is collected, and the precipitate is dried for 10-12 hours at 100-120 ℃ to obtain the modified nano silicon dioxide.
6. The fold-resistant anti-aging sole material of claim 1, wherein: the vulcanizing agent is elemental sulfur.
7. The fold-resistant anti-aging sole material of claim 1, wherein: the vulcanization accelerator is one of zinc oxide and stearic acid.
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