An antibacterial and odor-resistant shoe sole and its preparation method

Abstract

This invention relates to the field of shoe sole material technology, specifically disclosing an antibacterial and odor-resistant shoe sole and its preparation method. The shoe sole comprises polyisoprene rubber, styrene-butadiene rubber, cis-butadiene rubber, chitosan-based antibacterial agent, odor-resistant additive, and functional auxiliaries, achieving synergistic effects through specific formulations and processes. The chitosan-based antibacterial agent, with compounds containing quinoline and carbazole structures as its core, enhances the antibacterial effect by inhibiting the expression of bacterial surface proteins. The odor-resistant additive uses highly adsorbent activated carbon, bamboo charcoal, or diatomaceous earth, combined with a foaming and cross-linking system to optimize the shoe sole structure. This invention solves the problems of insufficient antibacterial performance, short-lived odor-resistant effect, and decreased mechanical properties in traditional shoe soles. Through component optimization and process control, it endows the shoe sole with long-lasting antibacterial and odor-resistant functions while maintaining excellent elasticity, abrasion resistance, and lightweight characteristics, making it suitable for footwear products with high hygiene requirements.

Description

Technical Field

[0001] This invention relates to the field of functional materials for shoe soles, specifically to an antibacterial and odor-resistant shoe sole and its preparation method. Background Technology

[0002] As people pay increasing attention to foot health, the functional requirements for shoe sole materials are becoming increasingly diversified. Traditional shoe sole materials mainly focus on basic properties such as abrasion resistance, elasticity, and lightweight. However, with the increasing complexity of footwear usage environments and rising demands for comfort and hygiene, antibacterial and odor-resistant functions are gradually becoming important indicators for shoe sole materials. Although various antibacterial and odor-resistant shoe sole materials have been developed, some problems still need to be addressed.

[0003] Existing antibacterial and odor-resistant shoe soles often lack sufficient antibacterial properties, especially under high humidity and prolonged use, where their antibacterial effect gradually weakens. Traditional antibacterial agents are mostly chemical substances such as silver ions and quaternary ammonium salts. These substances have poor dispersibility in shoe sole materials and are easily lost due to friction or washing, leading to a decline in antibacterial performance. In addition, some antibacterial agents have a narrow antibacterial spectrum and cannot effectively inhibit many common odor-causing bacteria (such as Staphylococcus aureus and Candida albicans), thus affecting the long-term antibacterial effect of the sole. Existing odor-resistant technologies mostly rely on adsorbent materials such as activated carbon and bamboo charcoal powder. Although these materials can adsorb odor molecules, their adsorption capacity is limited and cannot fundamentally inhibit bacterial growth. Once adsorption is saturated, the odor-resistant effect drops rapidly, failing to meet the hygiene requirements for long-term use. Furthermore, the addition of adsorbent materials often affects the elasticity and abrasion resistance of the sole, leading to a decline in sole performance. The manufacturing process of existing antibacterial and odor-resistant shoe soles is complex and costly, and it is difficult to simultaneously achieve the comprehensive performance of materials (such as abrasion resistance, elasticity, and lightweight).

[0004] Therefore, it is necessary to develop a shoe sole that has significant antibacterial and deodorizing properties while maintaining excellent mechanical properties. Summary of the Invention

[0005] To address the aforementioned problems, this invention proposes an antibacterial and odor-resistant shoe sole and its preparation method. By employing the synergistic effect of a chitosan-based antibacterial agent and various functional additives, the antibacterial and odor-resistant properties of the shoe sole are significantly improved. Simultaneously, the preparation process is optimized to ensure that the shoe sole material maintains excellent mechanical properties while possessing long-lasting antibacterial and odor-resistant functions. This invention not only solves the problems of insufficient antibacterial performance, short-lived odor-resistant effect, and uneven material properties in existing technologies, but also provides a new technical path for the functional development of shoe sole materials.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: an antibacterial and odor-resistant shoe sole, comprising the following components by weight: 25-35 parts of polyisoprene rubber, 35-45 parts of styrene-butadiene rubber, 10-20 parts of cis-butadiene rubber, 2-8 parts of emulsifier, 8-15 parts of chitosan-based antibacterial agent, 5-12 parts of odor-resistant additive, 3-8 parts of foaming agent, 1-5 parts of crosslinking agent, 2-6 parts of abrasion-resistant agent, and 1-3 parts of pigment;

[0007] The chitosan-based antibacterial agent comprises a bacteriostatic agent, the structure of which is a compound shown in Formula 1:

[0008] Formula 1;

[0009] R1 in Equation 1 is selected from: , or ;

[0010] The R2 is selected from any one of the following: hydrogen, aryl groups with 5-10 carbon atoms, cycloalkyl groups with 3-8 carbon atoms, and deuterated aryl groups with 5-10 carbon atoms;

[0011] Or R2 is selected from any one of the following: halogenated, alkyl with 1-5 carbon atoms, aryl with 5-10 carbon atoms substituted with alkoxy with 1-5 carbon atoms, cycloalkyl with 3-8 carbon atoms, and deuterated aryl with 5-10 carbon atoms.

[0012] Alkoxyl Indicates the link site.

[0013] Furthermore, the structure of the antibacterial agent is any one of Formula 2, Formula 3 or Formula 4;

[0014] Formula 2; Formula 3; Equation 4;

[0015] R2 is selected from any one of the following: hydrogen, phenyl, naphthyl, anthracene, cyclopropane, cyclopentane, cyclohexane, deuterated phenyl, and deuterated naphthyl;

[0016] Or R2 is selected from any one of the following: phenyl, naphthyl, anthracene, cyclopropane, cyclopentane, cyclohexane, deuterated phenyl, deuterated naphthyl substituted with halogen, methyl, ethyl, tert-butyl, deuterated methyl, deuterated ethyl, deuterated tert-butyl substituted phenyl, naphthyl.

[0017] Furthermore, the antibacterial agent is selected from compounds with the following structures:

[0018] ; ; ; ; ; ; ; ; ; ; ; Where D represents deuterium.

[0019] Furthermore, the emulsifier is sodium dibutylnaphthalenesulfonate.

[0020] Furthermore, the deodorizing additive is one or more of activated carbon, bamboo charcoal powder, or diatomaceous earth, with a particle size range of 100-500 mesh.

[0021] Furthermore, the foaming agent is one or more of azodicarbonamide, sodium bicarbonate, or ammonium carbonate.

[0022] Furthermore, the crosslinking agent is one or more of dicumyl peroxide, sulfur, and triallyl isocyanurate.

[0023] Furthermore, the wear-resistant agent is one or more of carbon black, nano-silica, and adhesive powder.

[0024] Furthermore, the dye is one or more of iron oxide red, iron oxide yellow, iron oxide black, phthalocyanine blue, and phthalocyanine green.

[0025] Furthermore, the preparation method of the chitosan-based antibacterial agent is as follows: dissolve chitosan in a 0.2 mol / L acetic acid solution to form a chitosan-acetic acid solution with a concentration of 0.5-1 g / L, and dissolve the antibacterial agent in the chitosan-acetic acid solution at a concentration of 1-4 g / L at 40-50°C to obtain the chitosan-based antibacterial agent.

[0026] A method for preparing an antibacterial and odor-resistant shoe sole includes the following steps:

[0027] S1. Raw material pretreatment: The polyisoprene rubber, the styrene-butadiene rubber and the cis-butadiene rubber are respectively plasticized at 50-70℃ for 5-10 minutes;

[0028] S2. Initial mixing: Mix the plasticized polyisoprene rubber, styrene-butadiene rubber and cis-butadiene rubber at 80-90℃ and 40-60rpm for 3-5 minutes.

[0029] S3. Addition of functional additives: Add the emulsifier, chitosan-based antibacterial agent and deodorizing additive to the S2 compounding in sequence, and mix at 70℃-90℃ and 40-60rpm for 8-12 minutes.

[0030] S4. Mixing the foaming and crosslinking system: Add the foaming agent, crosslinking agent, wear-resistant agent and pigment, and mix at high speed at 120-140℃ and 60-80rpm for 5-8 minutes to obtain the compound.

[0031] S5. Sheeting and storage: After the compounded rubber is pressed into sheets, it is left to stand at room temperature for 24 hours;

[0032] S6. Compression foaming molding: Place the rubber material in the mold, preheat at 120-130℃ for 2 minutes, then raise the temperature to 160-170℃, and apply pressure of 10-15MPa for foaming and vulcanization for 20-25 minutes.

[0033] S7. Post-processing: After demolding and trimming, cure at 50℃ for 2 hours to obtain the finished product.

[0034] Furthermore, the method for synthesizing the antibacterial agent is as follows:

[0035] ;

[0036] Step 1: Quinoline-6-ol and 11-bromo-8H-benzofurano[2,3-c]carbazole were synthesized via Williamson synthesis to produce 11-(quinoline-6-oxy)-8H-benzofurano[2,3-c]carbazole.

[0037] Step 2: 11-(quinoline-6-oxy)-8H-benzofurano[2,3-c]carbazole was synthesized from 2-bromo-6-nitronaphthalene via a Buchwald-Hartwig arylation reaction;

[0038] Step 3: The 8-(6-nitronaphth-2-yl)-11-(quinoline-6-yloxy)-8H-benzofurano[2,3-c]carbazole nitro group is reduced to generate 6-(11-(quinoline-6-yloxy)-8H-benzofurano[2,3-c]carbazole-8-yl)naphth-2-amine;

[0039] Step 4: 6-(11-(quinoline-6-yloxy)-8H-benzofurano[2,3-c]carbazole-8-yl)naphth-2-amine undergoes different condensation reactions to obtain the target products (antimicrobial agent 1 to antimicrobial agent 48).

[0040] Furthermore, the use of the antibacterial agent, its pharmaceutically acceptable salt, prodrug, stable isotope derivative, isomer, solvate, or polymorph, or the pharmaceutical composition of the third aspect of the present invention, in the preparation of a medicament for the prevention and / or treatment of diseases related to antibacterial activity.

[0041] The antibacterial agent exerts its deodorizing effect by inhibiting the activity of Staphylococcus aureus and Escherichia coli.

[0042] The antibacterial agent inhibits the expression of penicillin-binding proteins (PBPs) on the surface of bacteria, thereby inhibiting Staphylococcus aureus and Escherichia coli and thus playing a role in deodorization.

[0043] Compared with the prior art, the beneficial effects of the present invention are:

[0044] 1. Significantly Enhanced Antibacterial Performance: This invention significantly improves the antibacterial performance of shoe soles through the synergistic effect of chitosan-based antibacterial agents and various functional additives. Experimental data show that the antibacterial rate (against Staphylococcus aureus) of Application Examples 1 to 9 all reached over 98%, far exceeding the 15.2% of Comparative Example 1 (without chitosan-based antibacterial agent). Furthermore, the antibacterial agent effectively inhibits the activity of Staphylococcus aureus and Escherichia coli by suppressing the expression of penicillin-binding proteins (PBPs) on the bacterial surface, thereby achieving long-lasting antibacterial function.

[0045] 2. Excellent Odor-Deterrent Effect: The odor-deterrent additives (such as diatomaceous earth and activated carbon) of this invention work synergistically with chitosan-based antibacterial agents, not only adsorbing odor molecules but also fundamentally inhibiting bacterial growth, thereby significantly improving the odor-deterrent effect. Experimental data show that the deodorization rate of the application example (for isovaleric acid) is close to 98%, while the deodorization rate of Comparative Example 2 (without added odor-deterrent agent) is only 29.5%, indicating that this invention has a significant advantage in odor-deterrent performance.

[0046] 3. Superior Abrasion Resistance: Through optimized formulation and process, the sole material of this invention exhibits excellent abrasion resistance. Experimental data shows that the abrasion loss rate in the application examples is generally low, while the abrasion loss rate in Comparative Example 3 (without emulsifier) ​​is as high as 0.50%. This indicates that the formulation of this invention can effectively improve the abrasion resistance of the sole and extend its service life.

[0047] 4. Environmental friendliness and biocompatibility: The chitosan-based antibacterial agent used in this invention is a natural polymer material with good biocompatibility and environmental friendliness, avoiding the environmental pollution and health risks that may be caused by traditional chemical antibacterial agents. At the same time, the chitosan-based antibacterial agent disperses well in shoe sole materials and is not easily washed away by friction or water, ensuring the long-term stability of its antibacterial properties. Attached Figure Description

[0048] Figure 1 This is the synthetic route for the antibacterial agent described in this invention.

[0049] Figure 2 This diagram shows the docking and binding sites between the antibacterial agent 1 and PBPs molecules described in this invention. Detailed Implementation

[0050] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0051] An antibacterial and odor-resistant shoe sole, wherein the polyisoprene rubber is selected from the following weight parts: 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, and 35 parts.

[0052] An antibacterial and odor-resistant shoe sole, wherein the styrene-butadiene rubber is selected from the following weight parts: 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, and 45 parts.

[0053] An antibacterial and odor-resistant shoe sole, wherein the butadiene rubber is selected from the following weight parts: 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, and 20 parts.

[0054] An antibacterial and odor-resistant shoe sole, wherein the emulsifier is selected from the following weight parts: 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, and 8 parts.

[0055] An antibacterial and odor-resistant shoe sole, wherein the chitosan-based antibacterial agent is selected from the following weight parts: 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts.

[0056] An antibacterial and odor-resistant shoe sole, wherein the odor-resistant additive is selected from the following weight parts: 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, and 12 parts.

[0057] An antibacterial and odor-resistant shoe sole, wherein the foaming agent is selected from the following weight parts: 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, and 8 parts.

[0058] An antibacterial and odor-resistant shoe sole, wherein the crosslinking agent is selected from the following weight parts: 1 part, 2 parts, 3 parts, 4 parts, and 5 parts.

[0059] An antibacterial and odor-resistant shoe sole, wherein the abrasion-resistant agent is selected from the following proportions by weight: 2 parts, 3 parts, 4 parts, 5 parts, and 6 parts.

[0060] An antibacterial and odor-resistant shoe sole, wherein the pigment is selected from the following proportions by weight: 1 part, 2 parts, or 3 parts.

[0061] Example 1-1

[0062] Synthesis of intermediate: 6-(11-(quinolin-6-yloxy)-8H-benzofurano[2,3-c]carbazole-8-yl)naphthyl-2-amine:

[0063] ;

[0064] 20 g of quinoline-6-ol was dissolved in 200 mL of dimethyl sulfoxide, and 36.51 g of sodium bicarbonate was added. After stirring at room temperature for 30 min, 50.95 g of 11-bromo-8H-benzofurano[2,3-c]carbazole was added. The mixture was heated to 90 °C and reacted for 24 h. After cooling to room temperature, 80 mL of water was added, and a large amount of solid precipitated. The solid was filtered to obtain a white solid. The white solid was dissolved in 75 g of ethanol, stirred and refluxed at 90 °C for 3 h, filtered, and dried. The dried solid was purified by silica gel column chromatography, with ethyl acetate and petroleum ether as eluents, finally yielding 39.47 g of 11-(quinoline-6-oxy)-8H-benzofurano[2,3-c]carbazole. HPLC showed a purity of 99.8% and a yield of 71.54%. MS (MS+1): 401.

[0065] Under nitrogen protection, 39.47 g of 11-(quinoline-6-oxy)-8H-benzofurano[2,3-c]carbazole and 24.85 g of 2-bromo-6-nitronaphthalene were dissolved in 400 g of toluene solution. 18.95 g of sodium tert-butoxide, 0.3 g of tris(dibenzylacetone)dipalladium, and 2.0 g of tri-tert-butylphosphine were added. After stirring until homogeneous, the mixture was heated to 100 °C and refluxed for 12 h. After the reaction was complete, the temperature was slightly lowered, and the mixture was filtered through diatomaceous earth to remove salts and catalyst. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate; the organic phases were combined and dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the product was dissolved in petroleum ether / ethanol, recrystallized, filtered, and the filter cake was washed several times with petroleum ether and dried in a 60°C oven for 7 h to obtain 44.12 g of 8-(6-nitronaphth-2-yl)-11-(quinoline-6-yloxy)-8H-benzofurano[2,3-c]carbazole. HPLC showed a purity of 99.9% and a yield of 78.31%. MS (MS+1): 572.

[0066] 13.39 g of ammonium chloride was dissolved in 130 ml of water to prepare an ammonium chloride solution. 44.12 g of 8-(6-nitronaphth-2-yl)-11-(quinoline-6-yloxy)-8H-benzofurano[2,3-c]carbazole was dissolved in 500 ml of 95% ethanol, and then the prepared ammonium chloride solution was added. The mixture was heated to 85 °C, and after observing a clear reflux state, 16.51 g of iron powder was added. Reflux was continued for 2 hours, followed by filtration through diatomaceous earth. The filtrate was subjected to reduced pressure to remove the solvent, yielding a dry solid. The dried solid was added to 100 g of petroleum ether and refluxed for 3 h. After drying, the solid was purified by silica gel column chromatography with ethyl acetate and petroleum ether as eluents to obtain 31.30 g of 6-(11-(quinolin-6-yloxy)-8H-benzofurano[2,3-c]carbazole-8-yl)naphthyl-2-amine. HPLC showed a purity of 99.9% and a yield of 74.88%. MS (MS+1): 542.

[0067] 6-(11-(quinolin-6-yloxy)-8H-benzofurano[2,3-c]carbazole-8-yl)naphthyl-2-amine 1 H NMR, 400 MHz, deuterated chloroform: 8.90 (dd, 1H), 8.10-8.02 (m, 3H), 7.73-7.60 (m, 5H), 7.59-7.44 (m, 1H), 7.48-7.38 (m, 4H), 7.38-7.21 (m, 3H), 7.14 (dd, 1H), 7.04-6.89 (m, 3H), 4.09 (s, 2H). Example 1

[0068] Synthesis of antibacterial agent 1:

[0069] ;

[0070] Dissolve 7.58 g of 1-(phenylcarbamoyl)cyclopropane-1-carboxylic acid in 50 g of N,N-dimethylformamide, add 28.08 g of 2-(7-azobenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphate, and add 14.32 g of N,N-diisopropylethylamine under ice bath conditions. After reacting in an ice bath for 30 min, 20.00 g of 6-(11-(quinoline-6-yloxy)-8H-benzofurano[2,3-c]carbazole-8-yl)naphthyl-2-amine was added. The mixture was heated to 60 °C and reacted for 24 h. The reaction solution was diluted with ethyl acetate and extracted in water. The organic layer was dried with anhydrous sodium sulfate and the solvent was removed under reduced pressure to obtain a dry solid. The dry solid was added to 20 g of petroleum ether and refluxed for 3 h. The mixture was then evaporated to dryness. The residue was subjected to silica gel column chromatography with ethyl acetate and petroleum ether as the eluent to obtain the target product, a white solid of 8.49 g, with a yield of 31.54%. HPLC showed a purity of 99.9%, and MS (MS+1): 729.

[0071] Antibacterial agent 1 1 H NMR, 400 MHz, deuterated chloroform: 8.99 (s, 1H), 8.90 (dd, 1H), 8.88 (s, 1H), 8.15–8.09 (m, 1H), 8.09–8.02 (m, 3H), 7.93–7.82 (m, 2H), 7.79–7.72 (m, 1H), 7.71–7.60 (m, 2H), 7.56 (dd, 1H) ),7.54-7.47(m,2H),7.51-7.43(m,4H),7.47-7.36(m,4H),7.40-7.31(m,1H),7.34- 7.26(m,1H),7.18-7.10(m,2H),6.95(dd,1H),1.95-1.84(m,2H),1.70-1.58(m,2H).

[0072] The preparation method of the chitosan-based antibacterial agent 1 is as follows: chitosan is dissolved in a 0.2 mol / L acetic acid solution to form a chitosan-acetic acid solution with a concentration of 1 g / L. The antibacterial agent is then dissolved in the chitosan-acetic acid solution at a concentration of 2 g / L at 50°C to obtain the chitosan-based antibacterial agent 1. Example 2

[0073] The synthesis of antibacterial agent 2 was carried out according to the synthesis method of Example 1, wherein... Replace with The remaining feed ratios and post-treatment processes remained unchanged. MS (MS+1) of antibacterial agent 2: 785.

[0074] Chitosan-based antibacterial agent 2 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 3

[0075] The synthesis of antibacterial agent 9 was carried out according to the synthesis method in Example 1, wherein... Replace with The remaining feed ratios and post-treatment processes remained unchanged. MS (MS+1) of antibacterial agent 9: 735.

[0076] Chitosan-based antibacterial agent 3 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 4

[0077] The antibacterial agent 17 was synthesized according to the synthesis method in Example 1, wherein... Replace with The remaining feed ratios and post-treatment processes remained unchanged. MS (MS+1) of antibacterial agent 17: 646.

[0078] Chitosan-based antibacterial agent 4 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 5

[0079] The synthesis of antibacterial agent 24 was carried out according to the synthesis method of Example 1, wherein... Replace with The remaining feed ratios and post-treatment processes remained unchanged. MS (MS+1) of antibacterial agent 24: 711.

[0080] Chitosan-based antibacterial agent 5 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 6

[0081] The antibacterial agent 31 was synthesized according to the synthesis method in Example 1, wherein... Replace with The remaining feed ratios and post-treatment processes remained unchanged. MS (MS+1) of antibacterial agent 31: 696.

[0082] Chitosan-based antibacterial agent 6 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 7

[0083] The antibacterial agent 33 was synthesized according to the synthesis method in Example 1, wherein... Replace with The remaining feed ratios and post-treatment processes remained unchanged. MS (MS+1) of antibacterial agent 33: 661.

[0084] Chitosan-based antibacterial agent 7 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 8

[0085] The antibacterial agent 37 was synthesized according to the synthesis method in Example 1, wherein... Replace with The remaining feed ratios and post-treatment processes remained unchanged. MS (MS+1) of antibacterial agent 37: 739.

[0086] Chitosan-based antibacterial agent 8 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 9

[0087] The antibacterial agent 48 was synthesized according to the synthesis method in Example 1, wherein... Replace with The remaining feed ratios and post-treatment processes remained unchanged. MS (MS+1) of antibacterial agent 48: 739.

[0088] Chitosan-based antibacterial agent 9 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1.

[0089] Performance Test 1:

[0090] ①The docking binding energies of the compounds prepared in Examples 1 to 9 with PBPs molecules are shown in Table 1.

[0091] Table 1

[0092] Example PBP binding energy (kcal / mol) Example 1 -9.5 Example 2 -11.3 Example 3 -10.2 Example 4 -9.8 Example 5 -10.0 Example 6 -10.8 Example 7 -9.5 Example 8 -10.3 Example 9 -11.0

[0093] Application Example 1

[0094] A method for preparing an antibacterial and odor-resistant shoe sole includes the following steps:

[0095] S1. Raw material pretreatment: The 25 parts of polyisoprene rubber, the 25 parts of styrene-butadiene rubber and the 10 parts of cis-butadiene rubber are respectively plasticized at 70°C for 10 minutes;

[0096] S2. Initial mixing: Mix the plasticized polyisoprene rubber, styrene-butadiene rubber and cis-butadiene rubber at 90°C and 40 rpm for 5 minutes.

[0097] S3. Addition of functional additives: Add 4 parts of sodium dibutylnaphthalenesulfonate, 10 parts of chitosan-based antibacterial agent 1 (prepared in Example 1) and 12 parts of diatomaceous earth to the S2 mixture in sequence, and mix at 90°C and 60 rpm for 12 minutes.

[0098] S4. Mixing of foaming and crosslinking system: Add 4 parts sodium bicarbonate, 5 parts sulfur, 6 parts nano silica and 1 part iron oxide yellow, and mix at high speed at 140°C and 80 rpm for 8 minutes to obtain the compound.

[0099] S5. Sheeting and storage: After the compounded rubber is pressed into sheets, it is left to stand at room temperature for 24 hours;

[0100] S6. Compression foaming molding: Place the rubber material in the mold, preheat at 130℃ for 2 minutes, then raise the temperature to 170℃, apply pressure of 15MPa for foaming and vulcanization for 25 minutes;

[0101] S7. Post-processing: After demolding and trimming, cure at 50℃ for 2 hours to obtain the finished product.

[0102] Application Example 2

[0103] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with chitosan-based antibacterial agent 2 (prepared in Example 2), while the rest remained unchanged.

[0104] Application Example 3

[0105] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with chitosan-based antibacterial agent 3 (prepared in Example 3), while the rest remained unchanged.

[0106] Application Example 4

[0107] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with chitosan-based antibacterial agent 4 (prepared in Example 4), while the rest remained unchanged.

[0108] Application Example 5

[0109] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with chitosan-based antibacterial agent 5 (prepared in Example 5), while the rest remained unchanged.

[0110] Application Example 6

[0111] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with chitosan-based antibacterial agent 6 (prepared in Example 6), while the rest remained unchanged.

[0112] Application Example 7

[0113] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with chitosan-based antibacterial agent 7 (prepared in Example 7), while the rest remained unchanged.

[0114] Application Example 8

[0115] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with chitosan-based antibacterial agent 8 (prepared in Example 8), while the rest remained unchanged.

[0116] Application Example 9

[0117] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with chitosan-based antibacterial agent 9 (prepared in Example 9), while the rest remained unchanged.

[0118] Comparative Example 1

[0119] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 is not added, while the rest remains unchanged.

[0120] Comparative Example 2

[0121] Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the deodorizing agent is not added, and the rest remains unchanged.

[0122] Comparative Example 3

[0123] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the emulsifier was not added, and the rest remained unchanged.

[0124] Comparative Example 4

[0125] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the polyisoprene rubber is not added, and the rest remains unchanged.

[0126] Comparative Example 5

[0127] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 was replaced with the comparative antibacterial agent 1, while the rest remained unchanged.

[0128] The structure of the comparative antibacterial agent 1 is as follows: .

[0129] Comparative Example 6

[0130] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the antibacterial agent 1 is replaced with p-chlorobenzoic acid, while the rest remains unchanged.

[0131] Comparative Example 7

[0132] Referring to the preparation method of an antibacterial and odor-resistant shoe sole prepared in Application Example 1, the antibacterial agent is not added, and the rest remains unchanged.

[0133] Performance Test 2

[0134] The insole composite materials prepared in Application Examples 1-9 and Comparative Examples 1-4 of this invention were used to prepare samples that met the specifications. The antibacterial rate of the samples was tested according to GB / T 31402-2023 "Determination of antibacterial activity of plastics and other non-porous materials", with Staphylococcus aureus as the test species. The abrasion resistance of the samples was tested according to GB / T 5478-2008 "Plastics Rolling Abrasion Test Method". The samples were placed in sealed chambers, and then 60 ppm of isovaleric acid was introduced into the sealed chambers. After standing for 10 minutes, the residual gas concentration in each flask was detected by a TVOC detector after a specified time. The deodorization rate after the specified time was calculated. The specific test results are shown in Table 2.

[0135] Table 2

[0136] Sample number Antibacterial rate (%) (Staphylococcus aureus) Wear loss rate (%) (wear loss) Deodorization rate (%) (isovaleric acid, 10 min) Application Example 1 98.5 0.11 98.5 Application Example 2 98.3 0.12 98.2 Application Example 3 98.1 0.10 98.0 Application Example 4 98.2 0.09 98.3 Application Example 5 98.6 0.08 98.6 Application Example 6 98.4 0.13 98.4 Application Example 7 98.2 0.11 98.1 Application Example 8 98.5 0.12 98.3 Application Example 9 98.3 0.10 98.2 Comparative Example 1 15.2 0.19 41.3 Comparative Example 2 97.0 0.20 29.5 Comparative Example 3 93.7 0.50 85.2 Comparative Example 4 96.8 0.67 91.0 Comparative Example 5 77.1 0.14 98.2 Comparative Example 6 82.7 0.21 92.4 Comparative Example 7 62.4 0.17 80.3

[0137] The antibacterial and odor-resistant shoe soles prepared in Application Examples 1 to 9 exhibited excellent performance in terms of antibacterial rate (against Staphylococcus aureus), abrasion loss rate (abrasion loss), and deodorization rate (against isovaleric acid). Specifically, the antibacterial rate generally reached over 98%, the abrasion loss rate was low (between 0.08% and 0.13%), and the deodorization rate was also close to 98%. In contrast, Comparative Example 1 (without chitosan-based antibacterial agent) showed a significant decrease in both antibacterial and deodorization rates, and an increase in abrasion loss rate; Comparative Example 2 (without deodorizer) showed a significant decrease in deodorization rate; Comparative Example 3 (without emulsifier) ​​showed a significant increase in abrasion loss rate; and Comparative Example 4 (without polyisoprene rubber) showed a significant increase in abrasion loss rate (%), while the antibacterial rate decreased slightly but remained at a high level. Furthermore, Comparative Example 5 (replaced with a comparative antibacterial agent) showed antibacterial and deodorization rates close to those of the application examples, but a slightly higher abrasion loss rate. Overall, the formulation and process optimization of the application examples significantly improved the overall performance of the soles, while in contrast, the performance declined to varying degrees in cases where key components were not added or antibacterial agents were replaced.

[0138] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. An antibacterial and odor-resistant shoe sole, characterized in that, The composition includes the following components by weight: 25-35 parts polyisoprene rubber, 35-45 parts styrene-butadiene rubber, 10-20 parts cis-butadiene rubber, 2-8 parts emulsifier, 8-15 parts chitosan-based antibacterial agent, 5-12 parts deodorizing additive, 3-8 parts foaming agent, 1-5 parts crosslinking agent, 2-6 parts abrasion resistant agent, and 1-3 parts pigment. The chitosan-based antibacterial agent comprises a bacteriostatic agent, the structure of which is a compound shown in Formula 1: R1 in Equation 1 is selected from: R2 is selected from any one of the following: hydrogen, aryl groups having 6-10 carbon atoms, and cycloalkyl groups having 3-8 carbon atoms; Or R2 is selected from: an aryl group having 6-10 substituted carbon atoms, or a cycloalkyl group having 3-8 substituted carbon atoms, wherein the substituent is any one of a halogen, an alkyl group having 1-5 carbon atoms, or an alkoxy group having 1-5 carbon atoms; in Indicates the link site; The emulsifier is sodium dibutylnaphthalene sulfonate; The deodorizing additive is one or more of activated carbon, bamboo charcoal powder or diatomaceous earth, with a particle size range of 100-500 mesh. The preparation method of the chitosan-based antibacterial agent is as follows: chitosan is dissolved in a 0.2 mol / L acetic acid solution to form a chitosan-acetic acid solution with a concentration of 0.5-1 g / L, and the antibacterial agent is dissolved in the chitosan-acetic acid solution at a concentration of 1-4 g / L at 40-50℃ to obtain the chitosan-based antibacterial agent.

2. The antibacterial and odor-resistant shoe sole according to claim 1, characterized in that, The structure of the antibacterial agent is any one of Formula 2, Formula 3 or Formula 4; R2 is selected from any one of the following: hydrogen, phenyl, naphthyl, cyclopropane, cyclopentane, and cyclohexane; R2 may be selected from: substituted phenyl, substituted naphthyl, substituted cyclopropane, substituted cyclopentane, substituted cyclohexane, and the substituent may be any one of halogen, methyl, ethyl, tert-butyl, deuterated methyl, deuterated ethyl, or deuterated tert-butyl.

3. The antibacterial and odor-resistant shoe sole according to claim 1, characterized in that, The antibacterial agent is selected from compounds with the following structures:

4. The antibacterial and odor-resistant shoe sole according to claim 1, characterized in that, The foaming agent is one or more of azodicarbonamide, sodium bicarbonate, or ammonium carbonate.

5. The antibacterial and odor-resistant shoe sole according to claim 1, characterized in that, The crosslinking agent is one or more of dicumyl peroxide, sulfur, and triallyl isocyanurate.

6. The antibacterial and odor-resistant shoe sole according to claim 1, characterized in that, The wear-resistant agent is one or more of carbon black, nano-silica, and adhesive powder.

7. A method for preparing an antibacterial and odor-resistant shoe sole according to any one of claims 1-6, characterized in that, Includes the following steps: S1. Raw material pretreatment: The polyisoprene rubber, the styrene-butadiene rubber and the cis-butadiene rubber are respectively plasticized at 50-70℃ for 5-10 minutes; S2. Initial mixing: Mix the plasticized polyisoprene rubber, styrene-butadiene rubber and cis-butadiene rubber at 80-90℃ and 40-60rpm for 3-5 minutes. S3. Addition of functional additives: Add the emulsifier, chitosan-based antibacterial agent and deodorizing additive to the S2 compounding in sequence, and mix at 70℃-90℃ and 40-60rpm for 8-12 minutes. S4. Mixing the foaming and crosslinking system: Add the foaming agent, crosslinking agent, wear-resistant agent and pigment, and mix at high speed at 120-140℃ and 60-80rpm for 5-8 minutes to obtain the compound. S5. Sheeting and storage: After the compounded rubber is pressed into sheets, it is left to stand at room temperature for 24 hours; S6. Compression foaming molding: Place the rubber material in the mold, preheat at 120-130℃ for 2 minutes, then raise the temperature to 160-170℃, and apply pressure of 10-15MPa for foaming and vulcanization for 20-25 minutes. S7. Post-processing: After demolding and trimming, cure at 50℃ for 2 hours to obtain the finished product.

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