Anti-aging sole material and preparation method thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to an anti-aging sole material and a preparation method thereof.The anti-aging sole material comprises, by weight, 60-80 parts of SBS, 20-30 parts of HNBR, 3-6 parts of an antibacterial agent, 12-14 parts of inorganic filler, 6-8 parts of softening oil, 3-5 parts of a silane coupling agent, 2-3 parts of a vulcanizing agent, 3-5 parts of a vulcanization accelerator, 2-6 parts of D230 polyether amine and 2-6 parts of a phenolic resin tanning agent. SBS comprises hydrogenated SBS and oil-filled SBS, the hydrogenated SBS and HNBR have a synergistic effect, the hydrogenated SBS converts a polybutadiene chain segment into a more stable polyethylene / polybutylene chain segment through hydrogenation saturated double bonds, and the ultraviolet aging resistance is remarkably improved; and a hydrogenated structure of HNBR further blocks an oxidation chain reaction, so that the tensile strength of the material after QUV aging is relatively high. The oil-filled SBS improves the processability, reduces the melt viscosity, improves the mixing efficiency, and maintains the elasticity of the material at the same time.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and particularly relates to an anti-aging sole material and a preparation method thereof. Background Art

[0002] Styrene-butadiene-styrene triblock thermoplastic elastomer (SBS) is a widely used thermoplastic elastomer. Compared to other thermoplastic elastomers, it is relatively inexpensive, has a stable product supply, and exhibits excellent physical and mechanical properties, good wear resistance, and superior processing properties. It is a widely used, high-performance polymer material. Compared to traditional rubber material processing, it eliminates the vulcanization step, simplifying the production process, improving the workshop environment, reducing the factory's investment in equipment and land, and lowering production costs. Furthermore, scraps from production can be recycled in a certain proportion, which helps reduce solid waste emissions and protect the environment. It is widely used as a sole material in the footwear industry.

[0003] The advantages of SBS as a shoe sole material include: 1. Its unique structural properties provide excellent anti-slip and rebound properties; 2. The resulting soles have minimal initial color variation; 3. Soles made with SBS blends exhibit minimal deformation under pressure, providing excellent foot comfort. SBS appears as a white or gold porous, round rod or granular flake. The molecular weight of linear SBS is generally 80-120,000, while that of star-shaped SBS is 140-300,000, with a relative density of 0.92-0.95. The SBS backbone exhibits excellent tensile strength, elasticity, minimal permanent deformation, flexural resistance, excellent rebound properties, a relatively high coefficient of friction, and excellent plastic processing properties. However, due to the large number of unsaturated double bonds in the backbone, SBS is not resistant to oxidation and is prone to discoloration under UV exposure. Antioxidants and UV absorbers are often added to protect against UV damage, thereby extending the lifespan of SBS products. However, most shoes currently on the market made of SBS thermoplastic elastomers have poor weather resistance and wear resistance, and are prone to wear and tear, resulting in sole deformation. SBS modifications are primarily categorized into chemical and blending modifications, both aimed at improving the properties of existing SBS. SBS triblock copolymers comprise polystyrene (PS) and polybutadiene (PB) blocks, with the PS blocks serving as physical crosslinks. At room temperature, the PS blocks are glassy, ​​imparting solubility and thermoplasticity, while the PB blocks impart softness and resilience. This combination of characteristics gives SBS elasticity similar to that of vulcanized rubber. At high temperatures, the PS blocks exhibit a viscous flow, destroying the physical crosslinks and enabling plasticization and molding. As an adhesive, SBS exhibits excellent weather resistance and can be used over a wide temperature range. It is easily soluble in solvents and exhibits low solution viscosity, resulting in excellent production and application performance, superior bonding properties, rapid curing, and ease of application. It can be formulated into a variety of adhesives. However, since SBS is a non-polar material, its application in bonding polar materials is limited.

[0004] Titanium dioxide, the whitest substance in the world, is a wide-bandgap transparent metal oxide semiconductor with three common crystal structures: rutile, anatase, and brookite. Anatase and rutile are more common in nature. Both have optical band gaps above 3.0 eV and exhibit excellent photoinduced superhydrophilicity, photocatalytic properties, photocorrosion resistance, and antibacterial properties. Titanium dioxide is often used as a UV absorber in various materials. It absorbs in both the UVA and UVB bands. In addition to absorbing ultraviolet rays, it can also scatter them to a certain extent. However, nano-titanium dioxide has high surface energy, is prone to agglomeration, and is difficult to disperse in the matrix.

[0005] Currently, existing technologies focus more on the comfort of sole materials, often ignoring their folding resistance. In environments such as construction sites, workshops, and factories, sole materials must exhibit a certain degree of folding resistance, especially in environments where the soles are prone to cuts. Summary of the Invention

[0006] The purpose of the present invention is to overcome the above-mentioned problems existing in the traditional technology and provide an anti-aging sole material and a preparation method thereof.

[0007] In order to achieve the above technical objectives and the above technical effects, the present invention is implemented through the following technical solutions: The present invention provides an anti-aging sole material, comprising the following components in parts by weight: 60-80 parts of SBS, 20-30 parts of HNBR, 3-6 parts of an antibacterial agent, 12-14 parts of an inorganic filler, 6-8 parts of a softening oil, 3-5 parts of a silane coupling agent, 2-3 parts of a vulcanizing agent, 3-5 parts of a vulcanization accelerator, 2-6 parts of D230 polyetheramine, and 2-6 parts of a phenolic resin tanning agent; The antibacterial agent is prepared by mixing modified nano titanium dioxide and nano zinc oxide in a mass ratio of 1 to 2:1.

[0008] Furthermore, the SBS is formed by mixing hydrogenated SBS and oil-extended SBS in a mass ratio of 1 to 3:1; wherein the hydrogenated SBS converts polybutadiene segments into polyethylene and polybutene segments by hydrogenating saturated double bonds; and the oil-extended SBS is added with 30 to 33 wt% of naphthenic oil.

[0009] Furthermore, the preparation method of the modified nano-titanium dioxide comprises the following steps: 1) Mix 12-15 g of titanium dioxide with 35 mL of deionized water and 25 mL of propylene glycol. Adjust the pH to 9.5 ± 0.2 with 0.8 mol / L NaOH. Stir in a 60°C water bath with magnetic stirring to form a slurry. Disperse the mixture under 40 kHz, 200 W ultrasound for 15-20 min. 2) Add 0.15g of nano-SiO2 and 0.4g of γ-Al2O3 in stages and treat with a high-speed shear emulsifier for 45 minutes; introduce 0.5g of sodium polyacrylate and 0.2g of betaine as composite modifiers and react at 65°C and 50Hz ultrasonic environment for 1-1.5 hours; 3) Simultaneously add 0.8-1.2 g of triethoxyoctylsilane and 0.3 g of titanate coupling agent, and react at 80°C under nitrogen protection for 2-2.5 hours; 4) Spray drying is adopted, the inlet temperature of the spray drying is 180°C, the outlet temperature is 80°C, and the final product is obtained by air flow pulverization, and the particle size after pulverization is D50≤100nm.

[0010] Furthermore, the inorganic filler is montmorillonite or kaolin.

[0011] Furthermore, the softened oil is white oil.

[0012] Furthermore, the vulcanizing agent is elemental sulfur.

[0013] Furthermore, the vulcanization accelerator is stearic acid.

[0014] The present invention also provides a method for preparing an anti-aging sole material, comprising the following steps: S1. Mix nano-titanium dioxide and nano-zinc oxide, add a silane coupling agent, and process them in a ball mill at a speed of 300-500 r / min for 40-60 min to form a uniformly dispersed composite antibacterial agent; S2. Premix SBS and HNBR in an internal mixer at 110-120°C for 3-5 minutes, add softening oil to improve fluidity, then add the composite antibacterial agent and continue mixing for 4 minutes until completely dispersed; S3, adding the inorganic filler, D230 polyetheramine and phenolic resin tanning agent into an internal mixer in sequence, mixing at 105° C. until uniform, adding the vulcanizing agent and vulcanization accelerator at 90-95° C. to obtain a rubber compound; S4. After the rubber compound is extruded into granules by a twin-screw extruder, it is injected into the mold for segmented vulcanization: The first stage: preheat at 160℃ for 3 minutes and exhaust twice; The second stage: main vulcanization at 170℃ for 8-10min, pressure 15MPa; The third stage: demoulding at 60℃.

[0015] The beneficial effects of the present invention are: 1. The SBS in this invention includes hydrogenated SBS and oil-extended SBS. Hydrogenated SBS works synergistically with HNBR. Hydrogenated SBS converts polybutadiene segments into more stable polyethylene / polybutylene segments by hydrogenating saturated double bonds, significantly improving UV resistance. The hydrogenated structure of HNBR further blocks oxidative chain reactions, resulting in a tensile strength retention of >85% after 500 hours of QUV aging. Oil-extended SBS improves processability, while the 30-33% naphthenic oil content reduces melt viscosity, improving mixing efficiency, and maintaining material elasticity.

[0016] 2. In the present invention, the phenolic resin tanning agent is compounded with D230 polyetheramine. The phenolic resin tanning agent captures free radicals, and the D230 polyetheramine enhances the interfacial bonding force. The two synergistically delay the thermal oxidative aging of the material.

[0017] 3. The present invention adopts modified nano-TiO2 / ZnO composite antibacterial agent. Through silane coupling agent modification and ultrasonic dispersion, the nanoparticles are evenly dispersed and stably combined, achieving dual sterilization of photocatalysis (TiO2) and ion sustained release (ZnO), and the 24-hour antibacterial rate against Staphylococcus aureus is ≥99%.

[0018] 4. This invention contains no heavy metals. It utilizes an elemental sulfur vulcanization system, avoiding the toxicity risks associated with traditional lead salt stabilizers. Montmorillonite / kaolin reinforcement optimizes mechanical and processing properties, while layered silicate fillers activated with silane coupling agents enhance tensile strength (≥35kN / m) and tear resistance.

[0019] 5. The sole material prepared by the present invention has the characteristics of anti-aging, antibacterial, high strength and toughness, and easy processing, and is suitable for outdoor sports shoes and medical protective soles.

[0020] Of course, any product implementing the present invention does not necessarily need to achieve all of the above advantages at the same time. DETAILED DESCRIPTION

[0021] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention. Example

[0022] An anti-aging sole material comprises the following components in parts by weight: 60 parts of SBS, 30 parts of HNBR, 3 parts of an antibacterial agent, 14 parts of an inorganic filler, 6 parts of a softening oil, 5 parts of a silane coupling agent, 2 parts of a vulcanizing agent, 5 parts of a vulcanization accelerator, 2 parts of a D230 polyetheramine, and 6 parts of a phenolic resin tanning agent; The antibacterial agent is made of modified nano-titanium dioxide and nano-zinc oxide mixed in a mass ratio of 1:1.

[0023] In this embodiment, SBS is prepared by mixing hydrogenated SBS and oil-extended SBS in a mass ratio of 1:1. The hydrogenated SBS converts polybutadiene segments into polyethylene and polybutene segments by hydrogenating saturated double bonds. The oil-extended SBS is added with 30 wt% of naphthenic oil.

[0024] In this embodiment, the preparation method of modified nano-titanium dioxide includes the following steps: 1) Mix 12 g of titanium dioxide with 35 mL of deionized water and 25 mL of propylene glycol. Adjust the pH to 9.5 ± 0.2 with 0.8 mol / L NaOH. Stir in a 60°C water bath with magnetic stirring to form a slurry. Disperse the mixture under 40 kHz, 200 W ultrasound for 20 min. 2) Add 0.15g of nano-SiO2 and 0.4g of γ-Al2O3 in stages and treat with a high-speed shear emulsifier for 45 minutes; introduce 0.5g of sodium polyacrylate and 0.2g of betaine as composite modifiers and react at 65°C and 50Hz ultrasonic environment for 1 hour; 3) Simultaneously add 1.2 g of triethoxyoctylsilane and 0.3 g of titanate coupling agent, and react at 80 ° C for 2 h under nitrogen protection; 4) Spray drying is adopted, the inlet temperature of the spray drying is 180°C, the outlet temperature is 80°C, and the final product is obtained by air flow pulverization, and the particle size after pulverization is D50≤100nm.

[0025] In this embodiment, the inorganic filler is montmorillonite or kaolin.

[0026] In this embodiment, the softened oil is white oil.

[0027] In this embodiment, the vulcanizing agent is elemental sulfur.

[0028] In this embodiment, the vulcanization accelerator is stearic acid.

[0029] The present invention also provides a method for preparing an anti-aging sole material, comprising the following steps: S1, mixing nano titanium dioxide and nano zinc oxide, adding silane coupling agent, and processing through a ball mill at a speed of 300r / min for 60min to form a uniformly dispersed composite antibacterial agent; S2. Premix SBS and HNBR in an internal mixer at 110°C for 5 minutes, add softening oil to improve fluidity, then add the composite antibacterial agent and continue mixing for 4 minutes until completely dispersed; S3, adding the inorganic filler, D230 polyetheramine and phenolic resin tanning agent into an internal mixer in sequence, mixing at 105° C. until uniform, adding a vulcanizing agent and a vulcanization accelerator at 90° C. to obtain a rubber compound; S4. After the rubber compound is extruded into granules by a twin-screw extruder, it is injected into the mold for segmented vulcanization: The first stage: preheat at 160℃ for 3 minutes and exhaust twice; The second stage: main vulcanization at 170℃ for 8 minutes, pressure 15MPa; The third stage: demoulding at 60℃. Example

[0030] An anti-aging sole material comprises the following components in parts by weight: 80 parts of SBS, 20 parts of HNBR, 6 parts of an antibacterial agent, 12 parts of an inorganic filler, 8 parts of a softening oil, 3 parts of a silane coupling agent, 3 parts of a vulcanizing agent, 3 parts of a vulcanization accelerator, 6 parts of D230 polyetheramine, and 2 parts of a phenolic resin tanning agent; The antibacterial agent is made of modified nano-titanium dioxide and nano-zinc oxide in a mass ratio of 2:1.

[0031] In this embodiment, SBS is prepared by mixing hydrogenated SBS and oil-extended SBS in a mass ratio of 3:1. The hydrogenated SBS converts polybutadiene segments into polyethylene and polybutene segments by hydrogenating saturated double bonds. The oil-extended SBS is added with 33 wt% of naphthenic oil.

[0032] In this embodiment, the preparation method of modified nano-titanium dioxide includes the following steps: 1) Mix 15 g of titanium dioxide with 35 mL of deionized water and 25 mL of propylene glycol. Adjust the pH to 9.5 ± 0.2 with 0.8 mol / L NaOH. Stir in a 60°C water bath with magnetic stirring to form a slurry. Disperse the mixture under 40 kHz, 200 W ultrasound for 15 min. 2) Add 0.15g of nano-SiO2 and 0.4g of γ-Al2O3 in stages and treat with a high-speed shear emulsifier for 45 minutes; introduce 0.5g of sodium polyacrylate and 0.2g of betaine as composite modifiers and react at 65°C and 50Hz ultrasonic environment for 1.5 hours; 3) Simultaneously add 0.8 g of triethoxyoctylsilane and 0.3 g of titanate coupling agent, and react at 80 ° C for 2.5 h under nitrogen protection; 4) Spray drying is adopted, the inlet temperature of the spray drying is 180°C, the outlet temperature is 80°C, and the final product is obtained by air flow pulverization, and the particle size after pulverization is D50≤100nm.

[0033] In this embodiment, the inorganic filler is montmorillonite or kaolin.

[0034] In this embodiment, the softened oil is white oil.

[0035] In this embodiment, the vulcanizing agent is elemental sulfur.

[0036] In this embodiment, the vulcanization accelerator is stearic acid.

[0037] The present invention also provides a method for preparing an anti-aging sole material, comprising the following steps: S1, mixing nano titanium dioxide and nano zinc oxide, adding silane coupling agent, and processing through a ball mill at a speed of 500r / min for 40min to form a uniformly dispersed composite antibacterial agent; S2. Premix SBS and HNBR in an internal mixer at 120°C for 3 minutes, add softening oil to improve fluidity, then add the composite antibacterial agent and continue mixing for 4 minutes until completely dispersed; S3, adding the inorganic filler, D230 polyetheramine and phenolic resin tanning agent into an internal mixer in sequence, mixing at 105° C. until uniform, adding a vulcanizing agent and a vulcanization accelerator at 95° C. to obtain a rubber compound; S4. After the rubber compound is extruded into granules by a twin-screw extruder, it is injected into the mold for segmented vulcanization: The first stage: preheat at 160℃ for 3 minutes and exhaust twice; The second stage: main vulcanization at 170℃ for 10min, pressure 15MPa; The third stage: demoulding at 60℃. Example

[0038] An anti-aging sole material comprises the following components in parts by weight: 70 parts of SBS, 25 parts of HNBR, 4 parts of an antibacterial agent, 13 parts of an inorganic filler, 7 parts of a softening oil, 4 parts of a silane coupling agent, 2 parts of a vulcanizing agent, 4 parts of a vulcanization accelerator, 4 parts of a D230 polyetheramine, and 4 parts of a phenolic resin tanning agent; The antibacterial agent is made of modified nano-titanium dioxide and nano-zinc oxide mixed in a mass ratio of 1:1.

[0039] In this embodiment, SBS is prepared by mixing hydrogenated SBS and oil-extended SBS in a mass ratio of 2:1. The hydrogenated SBS converts polybutadiene segments into polyethylene and polybutene segments by hydrogenating saturated double bonds. The oil-extended SBS is added with 30-33 wt% of naphthenic oil.

[0040] In this embodiment, the preparation method of modified nano-titanium dioxide includes the following steps: 1) Mix 13 g of titanium dioxide with 35 mL of deionized water and 25 mL of propylene glycol. Adjust the pH to 9.5 ± 0.2 with 0.8 mol / L NaOH. Stir in a 60°C water bath with magnetic stirring to form a slurry. Disperse the mixture under 40 kHz, 200 W ultrasound for 18 min. 2) 0.15g of nano-SiO2 and 0.4g of γ-Al2O3 were added in stages and treated in a high-speed shear emulsifier for 45 minutes. 0.5g of sodium polyacrylate and 0.2g of betaine were introduced as composite modifiers and reacted at 65°C and 50Hz ultrasonic conditions for 1.3 hours. 3) Simultaneously add 1g of triethoxyoctylsilane and 0.3g of titanate coupling agent, and react at 80°C for 2.2h under nitrogen protection; 4) Spray drying is adopted, the inlet temperature of the spray drying is 180°C, the outlet temperature is 80°C, and the final product is obtained by air flow pulverization, and the particle size after pulverization is D50≤100nm.

[0041] In this embodiment, the inorganic filler is montmorillonite or kaolin.

[0042] In this embodiment, the softened oil is white oil.

[0043] In this embodiment, the vulcanizing agent is elemental sulfur.

[0044] In this embodiment, the vulcanization accelerator is stearic acid.

[0045] The present invention also provides a method for preparing an anti-aging sole material, comprising the following steps: S1, mixing nano titanium dioxide and nano zinc oxide, adding silane coupling agent, and processing through a ball mill at a speed of 400r / min for 50min to form a uniformly dispersed composite antibacterial agent; S2. Premix SBS and HNBR in an internal mixer at 115°C for 4 minutes, add softening oil to improve fluidity, then add the composite antibacterial agent and continue mixing for 4 minutes until completely dispersed; S3, adding the inorganic filler, D230 polyetheramine and phenolic resin tanning agent into an internal mixer in sequence, mixing at 105° C. until uniform, adding the vulcanizing agent and vulcanization accelerator at 92° C. to obtain a rubber compound; S4. After the rubber compound is extruded into granules by a twin-screw extruder, it is injected into the mold for segmented vulcanization: The first stage: preheat at 160℃ for 3 minutes and exhaust twice; The second stage: main vulcanization at 170℃ for 9 minutes and pressure of 15MPa; The third stage: demoulding at 60℃.

[0046] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An anti-aging sole material, characterized in that: The invention comprises the following components in parts by weight: 60 to 80 parts of SBS, 20 to 30 parts of HNBR, 3 to 6 parts of antibacterial agent, 12 to 14 parts of inorganic filler, 6 to 8 parts of softening oil, 3 to 5 parts of silane coupling agent, 2 to 3 parts of vulcanizing agent, 3 to 5 parts of vulcanization accelerator, 2 to 6 parts of D230 polyetheramine, and 2 to 6 parts of phenolic resin tanning agent; The antibacterial agent is prepared by mixing modified nano titanium dioxide and nano zinc oxide in a mass ratio of 1 to 2:

1.

2. The anti-aging sole material according to claim 1, characterized in that: The SBS is prepared by mixing hydrogenated SBS and oil-extended SBS in a mass ratio of 1 to 3:

1. The hydrogenated SBS converts polybutadiene segments into polyethylene and polybutene segments by hydrogenating saturated double bonds. The oil-extended SBS is added with 30 to 33 wt% of naphthenic oil.

3. The anti-aging sole material according to claim 1, characterized in that: The preparation method of the modified nano titanium dioxide comprises the following steps: 1) Mix 12-15 g of titanium dioxide with 35 mL of deionized water and 25 mL of propylene glycol. Adjust the pH to 9.5 ± 0.2 with 0.8 mol / L NaOH. Stir in a 60°C water bath with magnetic stirring to form a slurry. Disperse the mixture under 40 kHz, 200 W ultrasound for 15-20 min. 2) Add 0.15g of nano-SiO2 and 0.4g of γ-Al2O3 in stages and treat with a high-speed shear emulsifier for 45 minutes; introduce 0.5g of sodium polyacrylate and 0.2g of betaine as composite modifiers and react at 65°C and 50Hz ultrasonic environment for 1-1.5 hours; 3) Simultaneously add 0.8-1.2 g of triethoxyoctylsilane and 0.3 g of titanate coupling agent, and react at 80°C under nitrogen protection for 2-2.5 hours; 4) Spray drying is adopted, the inlet temperature of the spray drying is 180°C, the outlet temperature is 80°C, and the final product is obtained by air flow pulverization, and the particle size after pulverization is D50≤100nm.

4. The anti-aging sole material according to claim 1, characterized in that: The inorganic filler is montmorillonite or kaolin.

5. The anti-aging sole material according to claim 1, characterized in that: The softened oil is white oil.

6. The anti-aging sole material according to claim 1, characterized in that: The vulcanizing agent is elemental sulfur.

7. The anti-aging sole material according to claim 1, characterized in that: The vulcanization accelerator is stearic acid.

8. The method for preparing the anti-aging sole material according to any one of claims 1 to 7, characterized in that: The steps include: S1. Mix nano-titanium dioxide and nano-zinc oxide, add a silane coupling agent, and process them in a ball mill at a speed of 300-500 r / min for 40-60 min to form a uniformly dispersed composite antibacterial agent; S2. Premix SBS and HNBR in an internal mixer at 110-120°C for 3-5 minutes, add softening oil to improve fluidity, then add the composite antibacterial agent and continue mixing for 4 minutes until completely dispersed; S3, adding the inorganic filler, D230 polyetheramine and phenolic resin tanning agent into an internal mixer in sequence, mixing at 105° C. until uniform, adding the vulcanizing agent and vulcanization accelerator at 90-95° C. to obtain a rubber compound; S4. After the rubber compound is extruded into granules by a twin-screw extruder, it is injected into the mold for segmented vulcanization: The first stage: preheat at 160℃ for 3 minutes and exhaust twice; The second stage: main vulcanization at 170℃ for 8-10min, pressure 15MPa; The third stage: demoulding at 60℃.