Bacteriostatic deodorant sole and preparation method thereof

Abstract

The invention relates to the technical field of sole materials, and particularly discloses a bacteriostatic deodorant sole and a preparation method thereof. The sole comprises polyisoprene rubber, butadiene styrene rubber, butadiene rubber, a chitosan-based antibacterial agent, a deodorization additive and a functional aid, and synergistic interaction is realized through a specific ratio and a specific process. The chitosan-based antibacterial agent takes a compound containing a quinoline and carbazole structure as a core, and the antibacterial effect is enhanced by inhibiting bacterial surface protein expression; high-adsorbability activated carbon, bamboo charcoal or diatomite is selected as the deodorant additive, and the sole structure is optimized by combining foaming and crosslinking systems. The problems that a traditional shoe sole is insufficient in antibacterial performance, short in deodorization effect and reduced in mechanical property are solved, the shoe sole is endowed with long-acting antibacterial and deodorization functions through component optimization and process regulation and control, meanwhile, the excellent elasticity, wear resistance and lightweight characteristics are kept, and the shoe sole is suitable for shoe products with the high requirement for hygienic performance.

Description

Technical Field

[0001] The invention relates to the technical field of functional materials for soles, and in particular to an antibacterial and deodorizing sole and a preparation method thereof. Background Art

[0002] As people's awareness of foot health continues to grow, functional demands on sole materials are becoming increasingly diverse. Traditional sole materials primarily focus on basic properties such as wear resistance, elasticity, and lightweighting. However, with the increasing complexity of shoe usage environments and rising demands for comfort and hygiene, antibacterial and anti-odor properties are becoming increasingly important attributes for sole materials. While a variety of antibacterial and anti-odor sole materials have been developed, several challenges remain.

[0003] The antibacterial properties of existing antibacterial and deodorizing soles are often insufficient, especially in high humidity and with prolonged use, where the 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 the sole material and are easily lost due to friction or washing, resulting in a decrease in antibacterial performance. In addition, some antibacterial agents have a narrow antibacterial spectrum and are unable to 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 deodorizing technologies often rely on adsorptive materials such as activated carbon and bamboo charcoal powder. Although these materials can absorb odor molecules, their adsorption capacity is limited and they cannot fundamentally inhibit bacterial growth. Once adsorption reaches saturation, the deodorizing effect rapidly decreases, making it difficult to meet the hygienic requirements of long-term use. Furthermore, the addition of adsorptive materials often affects the elasticity and wear resistance of the sole, resulting in a decrease in sole performance. The preparation process of existing antibacterial and deodorizing soles is complex and costly, and the overall material properties (such as wear resistance, elasticity, and lightweight) are difficult to balance.

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

[0005] To address these issues, the present invention proposes an antibacterial and deodorizing shoe sole and its preparation method. By utilizing the synergistic effect of a chitosan-based antimicrobial agent and various functional additives, the antibacterial and deodorizing properties of the shoe sole are significantly enhanced. Simultaneously, the preparation process is optimized, ensuring that the sole material maintains excellent mechanical properties while also possessing long-lasting antibacterial and deodorizing properties. This invention not only addresses the existing issues of insufficient antibacterial performance, short-lived deodorizing effects, and uneven material properties, but also provides a new technical path for the functional development of shoe sole materials.

[0006] To achieve the above object, the technical solution adopted by the present invention is: an antibacterial and deodorizing shoe sole, comprising the following components in parts by weight: 25-35 parts of polyisoprene rubber, 35-45 parts of styrene-butadiene rubber, 10-20 parts of butadiene rubber, 2-8 parts of emulsifier, 8-15 parts of chitosan-based antibacterial agent, 5-12 parts of deodorizing additive, 3-8 parts of foaming agent, 1-5 parts of cross-linking agent, 2-6 parts of wear-resistant agent, and 1-3 parts of pigment; The components of the chitosan-based antibacterial agent include an antibacterial agent, and the structure of the antibacterial agent is a compound shown in Formula 1: Formula 1; R1 in Formula 1 is selected from: 、 or ; R2 is selected from any one of hydrogen, an aryl group having 5 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a deuterated aryl group having 5 to 10 carbon atoms; or R2 is selected from any one of: an aryl group having 5 to 10 carbon atoms substituted by a halogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a deuterated aryl group having 5 to 10 carbon atoms; Alkoxy Indicates the linking site.

[0007] Furthermore, the structure of the antibacterial agent is any one of Formula 2, Formula 3 or Formula 4; Formula 2; Formula 3; Formula 4; Wherein R2 is selected from any one of hydrogen, phenyl, naphthyl, anthracenyl, cyclopropane, cyclopentane, cyclohexane, deuterated phenyl, and deuterated naphthyl; Or R2 is selected from any one of phenyl, naphthyl, anthracenyl, cyclopropane, cyclopentane, cyclohexane, deuterated phenyl, and deuterated naphthyl substituted by halogen, methyl, ethyl, tert-butyl, deuterated methyl, deuterated ethyl, and deuterated tert-butyl.

[0008] Furthermore, the antibacterial agent is selected from the compounds described in the following structures: ; ; ; ; ; ; ; ; ; ; ; ; Wherein D represents deuterium.

[0009] Furthermore, the emulsifier is sodium dibutylnaphthalene sulfonate.

[0010] Furthermore, the deodorizing additive is one or more of activated carbon, bamboo charcoal powder or diatomaceous earth, and the particle size range is 100-500 mesh.

[0011] Furthermore, the foaming agent is one or more of azodicarbonamide, sodium bicarbonate or ammonium carbonate.

[0012] Furthermore, the cross-linking agent is one or more of dicumyl peroxide, sulfur, and triallyl isocyanurate.

[0013] Furthermore, the anti-wear agent is one or more of carbon black, nano-silicon dioxide, and rubber powder.

[0014] Furthermore, the dye is one or more of iron oxide red, iron oxide yellow, iron oxide black, phthalocyanine blue, and phthalocyanine green.

[0015] Furthermore, the preparation method of the chitosan-based antibacterial agent is as follows: dissolving 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 dissolving 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.

[0016] A method for preparing an antibacterial and deodorizing shoe sole comprises the following steps: S1. Raw material pretreatment: The polyisoprene rubber, the styrene-butadiene rubber and the butadiene rubber were masticated at 50-70 ° C for 5-10 minutes; S2 initial mixing: the plasticized polyisoprene rubber, styrene-butadiene rubber and butadiene rubber at 80-90 ℃, 40-60rpm mixing for 3-5 minutes; S3 functional additives are added: the emulsifier, chitosan-based antibacterial agent and deodorant additive are sequentially added to the mixing S2, and mixed at 70 ℃ -90 ℃, 40-60rpm for 8-12 minutes; S4 foaming and cross-linking system mixing: adding the foaming agent, cross-linking agent, wear agent and pigment, at 120-140 ℃, 60-80rpm high speed mixing for 5-8 minutes to obtain a rubber mix; S5. Sheet parking: The rubber mix was tableted and parked at room temperature for 24 hours; S6. Compression foaming: Place the rubber in a mold, preheat at 120-130°C for 2 minutes, then heat to 160-170°C, apply pressure of 10-15 MPa, and vulcanize for 20-25 minutes. S7. Post-processing: After demoulding and trimming, the finished product is cured at 50°C for 2 hours.

[0017] Furthermore, the synthesis method of the antibacterial agent is: ; Step 1: 11-(quinolin-6-oxy)-8H-benzofurano[2,3-c]carbazole is synthesized from quinolin-6-ol and 11-bromo-8H-benzofurano[2,3-c]carbazole via Williamson synthesis; Step 2: 11-(quinolin-6-yloxy)-8H-benzofurano[2,3-c]carbazole and 2-bromo-6-nitronaphthalene are reacted by Buchwald-Hartwig arylation to synthesize 8-(6-nitronaphthalene-2-yl)-11-(quinolin-6-yloxy)-8H-benzofurano[2,3-c]carbazole; Step 3: 8-(6-nitronaphthalene-2-yl)-11-(quinolin-6-yloxy)-8H-benzofurano[2,3-c]carbazole nitro group is reduced to generate 6-(11-(quinolin-6-yloxy)-8H-benzofurano[2,3-c]carbazole-8-yl)naphthalene-2-amine; Step 4: 6-(11-(quinolin-6-yloxy)-8H-benzofurano[2,3-c]carbazole-8-yl)naphthalene-2-amine was subjected to different condensation reactions to obtain the target products (antibacterial agents 1 to 48).

[0018] Furthermore, 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 is used in the preparation of a medicament for preventing and / or treating diseases related to antibacterial treatment.

[0019] The antibacterial agent plays an anti-odor role by inhibiting the activities of Staphylococcus aureus and Escherichia coli.

[0020] The antibacterial agent inhibits the expression of penicillin binding proteins (PBPs) on the surface of bacteria, thereby inhibiting Staphylococcus aureus and Escherichia coli and playing a role in deodorization.

[0021] Compared with the prior art, the present invention has the following beneficial effects: 1. Significantly Improved Antimicrobial Performance: This invention significantly enhances the antimicrobial performance of the shoe sole through the synergistic effect of a chitosan-based antimicrobial agent and various functional additives. Experimental data shows that the antimicrobial rates (against Staphylococcus aureus) in Application Examples 1 through 9 all exceeded 98%, significantly exceeding the 15.2% achieved in Comparative Example 1 (which lacked a chitosan-based antimicrobial agent). Furthermore, the antimicrobial 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 antimicrobial activity.

[0022] 2. Excellent deodorizing effect: The deodorizing additives (such as diatomaceous earth and activated carbon) of this invention work synergistically with the chitosan-based antimicrobial agent to not only absorb odor molecules but also fundamentally inhibit bacterial growth, significantly enhancing deodorizing effectiveness. Experimental data showed that the deodorizing rate (for isovaleric acid) in the application example was close to 98%, while the deodorizing rate in Comparative Example 2 (without deodorizing agent) was only 29.5%, demonstrating the significant advantages of this invention in deodorizing performance.

[0023] 3. Excellent Wear Resistance: Through optimized formulation and processing, the sole material of the present invention exhibits excellent wear resistance. Experimental data shows that the wear loss rate of the application examples is generally low, while the wear loss rate of Comparative Example 3 (no emulsifier added) is as high as 0.50%. This demonstrates that the formulation of the present invention can effectively improve the wear resistance of the sole and extend its service life.

[0024] 4. Environmental Protection and Biocompatibility: The chitosan-based antimicrobial agent used in this invention is a natural polymer material with excellent biocompatibility and environmental friendliness, avoiding the environmental pollution and health risks associated with traditional chemical antimicrobial agents. Furthermore, the chitosan-based antimicrobial agent is well dispersed in the sole material and is not easily lost due to friction or washing, ensuring the long-term stability of its antimicrobial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the synthetic route of the antibacterial agent of the present invention.

[0026] Figure 2 This is a diagram of the docking binding site between the antibacterial agent 1 described in the present invention and the PBPs molecule. DETAILED DESCRIPTION

[0027] The following will clearly and completely describe the technical solution of the present invention in conjunction with the accompanying drawings. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0028] An antibacterial and deodorizing shoe sole, wherein the polyisoprene rubber is selected from the following parts by weight: 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, and 35 parts.

[0029] An antibacterial and deodorizing shoe sole, wherein the styrene-butadiene rubber is selected from the following parts by weight: 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, and 45 parts.

[0030] An antibacterial and deodorizing shoe sole, wherein the butadiene rubber is selected from the following parts by weight: 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, and 20 parts.

[0031] An antibacterial and deodorizing shoe sole, wherein the emulsifier is selected from the following parts by weight: 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, and 8 parts.

[0032] An antibacterial and deodorizing shoe sole, wherein the chitosan-based antibacterial agent is selected from the following parts by weight: 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts.

[0033] An antibacterial and deodorizing shoe sole, wherein the deodorizing additive is selected from the group consisting of 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, and 12 parts by weight.

[0034] An antibacterial and deodorizing shoe sole, wherein the foaming agent is selected from the following parts by weight: 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, and 8 parts.

[0035] An antibacterial and deodorizing shoe sole, wherein the cross-linking agent is selected from the group consisting of 1 part, 2 parts, 3 parts, 4 parts, and 5 parts by weight.

[0036] An antibacterial and deodorizing shoe sole, wherein the wear-resistant agent is selected from the following parts by weight: 2 parts, 3 parts, 4 parts, 5 parts, and 6 parts.

[0037] An antibacterial and deodorizing shoe sole, wherein the pigment is selected from the group consisting of 1 part, 2 parts, and 3 parts by weight.

[0038] Example 1-1 Intermediate: Synthesis of 6-(11-(quinolin-6-yloxy)-8H-benzofurano[2,3-c]carbazol-8-yl)naphthalene-2-amine: ; Dissolve 20 g of quinolin-6-ol in 200 ml of dimethyl sulfoxide, add 36.51 g of sodium bicarbonate, and stir at room temperature for 30 minutes. Then, add 50.95 g of 11-bromo-8H-benzofurano[2,3-c]carbazole. Heat to 90°C for 24 hours, cool to room temperature, and then add 80 mL of water. A large amount of solid precipitates, which is filtered to obtain a white solid. The white solid is dissolved in 75 g of ethanol, stirred and refluxed at 90°C for 3 hours, filtered, and dried. The dried solid is purified by silica gel column chromatography using ethyl acetate and petroleum ether as eluents to obtain 39.47 g of 11-(quinolin-6-oxy)-8H-benzofurano[2,3-c]carbazole. HPLC analysis shows a purity of 99.8% and a yield of 71.54%. MS (MS+1) = 401.

[0039] 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, and 18.95 g of sodium tert-butoxide, 0.3 g of tris(dibenzylideneacetone)dipalladium and 2.0 g of tri-tert-butylphosphine were added. After stirring evenly, the temperature was raised to 100 ° C. and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered and filtered using diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed with water three times, and the organic phase was retained. , then the aqueous phase was extracted with ethyl acetate; after combining the organic phases, they were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the product was dissolved in petroleum ether / ethanol and recrystallized. After filtration, the filter cake was rinsed with petroleum ether several times and dried in a 60°C oven for 7 hours to obtain 44.12 g of 8-(6-nitronaphthalen-2-yl)-11-(quinolin-6-yloxy)-8H-benzofurano[2,3-c]carbazole. HPLC showed a purity of 99.9%, a yield of 78.31%, and MS (MS+1): 572.

[0040] Dissolve 13.39 g of ammonium chloride in 130 ml of water to prepare an ammonium chloride solution. Dissolve 44.12 g of 8-(6-nitronaphthalen-2-yl)-11-(quinolin-6-yloxy)-8H-benzofuro[2,3-c]carbazole in 500 ml of 95% ethanol and add the prepared ammonium chloride solution. Raise the temperature to 85°C. Once a clear reflux is observed, add 16.51 g of iron powder. Continue to reflux for 2 hours, then filter through celite. Remove the solvent from the filtrate under reduced pressure to obtain a dry solid. The dried solid was added to 100 g of petroleum ether, refluxed for 3 h, and then spin-dried. After spin-drying, it 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)naphthalene-2-amine. HPLC showed a purity of 99.9%, a yield of 74.88%, and MS (MS+1): 542.

[0041] 6-(11-(quinolin-6-yloxy)-8H-benzofuro[2,3-c]carbazol-8-yl)naphthalene-2-amine 1 HNMR, 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

[0042] Synthesis of antibacterial agent 1: ; 7.58 g of 1-(phenylcarbamoyl)cyclopropane-1-carboxylic acid was dissolved in 50 g of N,N-dimethylformamide, 28.08 g of 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate was added, and 14.32 g of N,N-diisopropylethylamine was added under ice cooling. After reacting in an ice bath for 30 minutes, 20.00 g of 6-(11-(quinolin-6-yloxy)-8H-benzofuran[2,3-c]carbazole-8-yl)naphthalene-2-amine was added, the temperature was raised to 60 ° C. and the reaction was reacted for 24 hours. The reaction solution was diluted with ethyl acetate and extracted with water. The organic layer was dried over 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 hours. After that, it was spin-dried. The residue was chromatographed on a silica gel column with ethyl acetate and petroleum ether as eluents to obtain the target product as a white solid (8.49 g). The yield was 31.54%. The purity was 99.9% according to HPLC, and MS (MS+1): 729.

[0043] Antibacterial agent 1 1 HNMR, 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).

[0044] The preparation method of the chitosan-based antibacterial agent 1 is as follows: dissolving chitosan in a 0.2 mol / L acetic acid solution to form a chitosan-acetic acid solution with a concentration of 1 g / L; and dissolving the antibacterial agent 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

[0045] The synthesis of antibacterial agent 2 was carried out by referring to the synthesis method of Example 1. Replace with The rest of the feed ratios and post-treatments remained unchanged. MS (MS+1) of antibacterial agent 2: 785.

[0046] Chitosan-based antibacterial agent 2 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 3

[0047] The synthesis of antibacterial agent 9 is as follows: Replace with The rest of the feed ratios and post-treatments remained unchanged. MS (MS+1) of antibacterial agent 9: 735.

[0048] Chitosan-based antibacterial agent 3 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 4

[0049] The synthesis of antibacterial agent 17 was carried out by referring to the synthesis method of Example 1. Replace with The rest of the feed ratios and post-treatments remained unchanged. MS (MS+1) of antibacterial agent 17: 646.

[0050] Chitosan-based antibacterial agent 4 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 5

[0051] The synthesis of antibacterial agent 24 was carried out by referring to the synthesis method of Example 1. Replace with The rest of the feed ratios and post-treatments remained unchanged. MS (MS+1) of antibacterial agent 24: 711.

[0052] Chitosan-based antibacterial agent 5 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 6

[0053] The synthesis of antibacterial agent 31 was carried out by referring to the synthesis method of Example 1. Replace with The rest of the feed ratios and post-treatments remained unchanged. MS (MS+1) of antibacterial agent 31: 696.

[0054] Chitosan-based antibacterial agent 6 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 7

[0055] The synthesis of antibacterial agent 33 was carried out by referring to the synthesis method of Example 1. Replace with The rest of the feed ratios and post-treatments remained unchanged. MS (MS+1) of antibacterial agent 33: 661.

[0056] Chitosan-based antibacterial agent 7 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 8

[0057] The synthesis of antibacterial agent 37 was carried out by referring to the synthesis method of Example 1. Replace with The rest of the feed ratios and post-treatments remained unchanged. The MS (MS+1) of antibacterial agent 37 was 739.

[0058] Chitosan-based antibacterial agent 8 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1. Example 9

[0059] The synthesis of antibacterial agent 48 was carried out by referring to the synthesis method of Example 1. Replace with The rest of the feed ratios and post-treatments remained unchanged. The MS (MS+1) of antibacterial agent 48 was 739.

[0060] Chitosan-based antibacterial agent 9 was prepared according to the preparation method of chitosan-based antibacterial agent 1 in Example 1.

[0061] Performance Test 1: ① The docking binding energies of the compounds prepared in Examples 1 to 9 with PBPs molecules are shown in Table 1.

[0062] Table 1 Example PBPs 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 Application Example 1 A method for preparing an antibacterial and deodorizing shoe sole comprises the following steps: S1. Raw material pretreatment: The 25 parts of polyisoprene rubber, the 25 parts of styrene-butadiene rubber and the 10 parts of butadiene rubber were masticated at 70 ° C for 10 minutes; S2 initial mixing: the plasticized polyisoprene rubber, styrene-butadiene rubber and butadiene rubber at 90 ° C, 40rpm mixing for 5 minutes; S3 functional additives are added: 4 parts of sodium dibutylnaphthalene sulfonate, 10 parts of chitosan-based antibacterial agent 1 (prepared in Example 1) and 12 parts of diatomaceous earth were sequentially added to the mixing S2, and mixed at 90 ° C, 60 rpm for 12 minutes; S4 foaming and cross-linking system mixing: adding 4 parts of sodium bicarbonate, 5 parts of sulfur, 6 parts of nano-silica and 1 part of yellow iron oxide, at 140 ° C, 80rpm high speed mixing for 8 minutes to obtain a rubber mix; S5. Sheet parking: The rubber mix was tableted and parked at room temperature for 24 hours; S6. Compression foaming: The rubber compound is placed in a mold, preheated at 130°C for 2 minutes, then heated to 170°C, and pressurized at 15MPa for 25 minutes. S7. Post-processing: After demoulding and trimming, the finished product is cured at 50°C for 2 hours.

[0063] Application Example 2 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with the chitosan-based antibacterial agent 2 (prepared in Example 2), and the rest remained unchanged.

[0064] Application Example 3 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with the chitosan-based antibacterial agent 3 (prepared in Example 3), and the rest remained unchanged.

[0065] Application Example 4 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with the chitosan-based antibacterial agent 4 (prepared in Example 4), and the rest remained unchanged.

[0066] Application Example 5 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with the chitosan-based antibacterial agent 5 (prepared in Example 5), and the rest remained unchanged.

[0067] Application Example 6 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with the chitosan-based antibacterial agent 6 (prepared in Example 6), and the rest remained unchanged.

[0068] Application Example 7 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with the chitosan-based antibacterial agent 7 (prepared in Example 7), and the rest remained unchanged.

[0069] Application Example 8 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with the chitosan-based antibacterial agent 8 (prepared in Example 8), and the rest remained unchanged.

[0070] Application Example 9 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 (prepared in Example 1) was replaced with the chitosan-based antibacterial agent 9 (prepared in Example 9), and the rest remained unchanged.

[0071] Comparative Example 1 Referring to the method for preparing an antibacterial and deodorizing shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 is not added, and the rest remains unchanged.

[0072] Comparative Example 2 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the deodorant is not added therein, and the rest remains unchanged.

[0073] Comparative Example 3 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the emulsifier is not added and the rest remains unchanged.

[0074] Comparative Example 4 Referring to the method for preparing an antibacterial and deodorizing shoe sole prepared in Application Example 1, the polyisoprene rubber is not added, and the rest remains unchanged.

[0075] Comparative Example 5 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the chitosan-based antibacterial agent 1 was replaced with the comparative antibacterial agent 1, and the rest remained unchanged.

[0076] The structure of the comparative antibacterial agent 1 is: .

[0077] Comparative Example 6 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the antibacterial agent 1 was replaced with p-chlorobenzoic acid, and the rest remained unchanged.

[0078] Comparative Example 7 Referring to the preparation method of an antibacterial and deodorizing shoe sole prepared in Application Example 1, the antibacterial agent is not added, and the rest remains unchanged.

[0079] Performance test 2 The insole composite materials prepared from Application Examples 1 to Application Examples 9 and Comparative Examples 1 to Comparative Examples 4 of the present invention were prepared into test samples that met the specifications. The antibacterial rates of the test samples were tested according to GB / T 31402-2023 "Determination of Antibacterial Activity on the Surfaces of Plastics and Other Non-porous Materials" using Staphylococcus aureus as the test strain. The wear resistance of the test samples was tested according to GB / T 5478-2008 "Test Method for Rolling Wear of Plastics." The test samples were placed in sealed boxes, and 60 ppm of isovaleric acid was introduced into the sealed boxes. The boxes were then allowed to stand for 10 minutes. The residual gas concentration in each flask after a specified period of time from the time of standing was measured using a TVOC detector, and the deodorization rate after the specified period of time was calculated. The specific test results are shown in Table 2: Table 2 Sample number Antibacterial rate (%) (Staphylococcus aureus) Wear loss rate (%) (wear loss) Deodorization rate (%) (isovaleric acid, 10min) 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 The antibacterial and deodorizing shoe soles prepared in Application Examples 1 to 9 demonstrated excellent performance in terms of antibacterial rate (against Staphylococcus aureus), wear loss rate (abrasion loss), and deodorization rate (against isovaleric acid). The antibacterial rate generally exceeded 98%, the abrasion loss rate was low (ranging from 0.08% to 0.13%), and the deodorization rate approached 98%. In contrast, the antibacterial and deodorization rates of Comparative Example 1 (without the addition of a chitosan-based antibacterial agent) decreased significantly, while the abrasion loss rate also increased. The deodorization rate of Comparative Example 2 (without the addition of a deodorant) decreased significantly, while the abrasion loss rate of Comparative Example 3 (without the addition of an emulsifier) ​​increased significantly. The abrasion loss rate of Comparative Example 4 (without the addition of polyisoprene rubber) increased significantly, while the antibacterial rate decreased slightly but remained high. Furthermore, the antibacterial and deodorization rates of Comparative Example 5 (with the comparison antibacterial agent) were close to those of the Application Examples, but the abrasion loss rate was slightly higher. Overall, the formula and process optimization of the application examples significantly improved the comprehensive performance of the soles. In comparison, for example, when no key components were added or the antibacterial agents were replaced, the performance declined to varying degrees.

[0080] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. An antibacterial and deodorizing sole, characterized in that: The following components are included in parts by weight: 25-35 parts of polyisoprene rubber, 35-45 parts of styrene-butadiene rubber, 10-20 parts of butadiene rubber, 2-8 parts of emulsifier, 8-15 parts of chitosan-based antibacterial agent, 5-12 parts of deodorizing additive, 3-8 parts of foaming agent, 1-5 parts of cross-linking agent, 2-6 parts of wear-resistant agent, and 1-3 parts of pigment; The components of the chitosan-based antibacterial agent include an antibacterial agent, and the structure of the antibacterial agent is a compound shown in Formula 1: Formula 1; R1 in Formula 1 is selected from: 、 or ; R2 is selected from any one of hydrogen, an aryl group having 5 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a deuterated aryl group having 5 to 10 carbon atoms; or R2 is selected from any one of: an aryl group having 5 to 10 carbon atoms substituted by a halogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a deuterated aryl group having 5 to 10 carbon atoms; Alkoxy Indicates the linking site.

2. The antibacterial and deodorizing 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; Formula 2; Formula 3; Formula 4; Wherein R2 is selected from any one of hydrogen, phenyl, naphthyl, anthracenyl, cyclopropane, cyclopentane, cyclohexane, deuterated phenyl, and deuterated naphthyl; Or R2 is selected from any one of phenyl, naphthyl, anthracenyl, cyclopropane, cyclopentane, cyclohexane, deuterated phenyl, and deuterated naphthyl substituted by halogen, methyl, ethyl, tert-butyl, deuterated methyl, deuterated ethyl, and deuterated tert-butyl.

3. The antibacterial and deodorizing sole according to claim 1, characterized in that: The antibacterial agent is selected from the compounds described in the following structures: ； ； ； ； ； ； ； ； ； ； ； ； Use of the bacteriostatic 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 preventing and / or treating diseases related to bacteriostasis.

4. The antibacterial and deodorizing sole according to claim 1, characterized in that: The emulsifier is sodium dibutylnaphthalene sulfonate.

5. The antibacterial and deodorizing sole according to claim 1, characterized in that: The deodorizing additive is one or more of activated carbon, bamboo charcoal powder or diatomaceous earth, and the particle size range is 100-500 meshes.

6. The antibacterial and deodorizing sole according to claim 1, characterized in that: The foaming agent is one or more of azodicarbonamide, sodium bicarbonate or ammonium carbonate.

7. The antibacterial and deodorizing sole according to claim 1, characterized in that: The cross-linking agent is one or more of dicumyl peroxide, sulfur, and triallyl isocyanurate.

8. The antibacterial and deodorizing sole according to claim 1, characterized in that: The anti-wear agent is one or more of carbon black, nano silicon dioxide and rubber powder.

9. The antibacterial and deodorizing sole according to claim 1, characterized in that: The preparation method of the chitosan-based antibacterial agent comprises the following steps: dissolving 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 dissolving 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.

10. A method for preparing an antibacterial and deodorizing shoe sole according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Raw material pretreatment: The polyisoprene rubber, the styrene-butadiene rubber and the butadiene rubber were masticated at 50-70 ° C for 5-10 minutes; S2 initial mixing: the plasticized polyisoprene rubber, styrene-butadiene rubber and butadiene rubber at 80-90 ℃, 40-60rpm mixing for 3-5 minutes; S3 functional additives are added: the emulsifier, chitosan-based antibacterial agent and deodorant additive are sequentially added to the mixing S2, and mixed at 70 ℃ -90 ℃, 40-60rpm for 8-12 minutes; S4 foaming and cross-linking system mixing: adding the foaming agent, cross-linking agent, wear agent and pigment, at 120-140 ℃, 60-80rpm high speed mixing for 5-8 minutes to obtain a rubber mix; S5. Sheet parking: The rubber mix was tableted and parked at room temperature for 24 hours; S6. Compression foaming: Place the rubber in a mold, preheat at 120-130°C for 2 minutes, then heat to 160-170°C, apply pressure of 10-15 MPa, and vulcanize for 20-25 minutes. S7. Post-processing: After demoulding and trimming, the finished product is cured at 50°C for 2 hours.

Images