An antibacterial and deodorizing foamed insole and its preparation method

Abstract

This invention discloses an antibacterial and deodorizing foamed insole and its preparation method, belonging to the technical field of layered products. The raw materials for this foamed insole include: Artemisia argyi, an aqueous ethanol solution, an oil-phase carrier, an aqueous solution of sodium dodecyl sulfate, an aqueous solution of methyl methacrylate (MMA) resin, citric acid solution, Tween-80, fumed silica, polyether polyol, crosslinking agent, composite catalyst, organosilicon foam stabilizer, water, and isocyanate. The preparation method includes: extraction and concentration of active ingredients from Artemisia argyi, preparation of modified biofunctional agents from Artemisia argyi, preparation of functional polyol components from Artemisia argyi, and polyurethane foaming molding and curing. Compared with existing technologies, this invention effectively inhibits the loss of volatile components of Artemisia argyi during high-temperature processing through the synergistic effect of the oil-phase carrier compound and the heat-stabilized carrier, significantly improving the antibacterial and deodorizing performance of the insole.

Description

Technical Field

[0001] This invention relates to the field of layered product technology, and in particular to an antibacterial and deodorizing foamed insole and its preparation method. Background Technology

[0002] Currently, the preparation of antibacterial and deodorizing foamed insoles mostly involves directly adding antibacterial or deodorizing agents to a polyurethane substrate. Common antibacterial agents include plant extracts, nano-silver, and quaternary ammonium salts, while deodorizing agents often rely on the physical adsorption of porous materials such as activated carbon and zeolite. Artemisia argyi, due to its natural antibacterial properties, is widely used in the insole industry. However, the volatile antibacterial components in Artemisia argyi are easily lost during the high-temperature processing of polyurethane foam, resulting in a short-lasting and insignificant antibacterial and deodorizing effect.

[0003] In the prior art, patent CN117770575A discloses an antibacterial and deodorizing polyurethane insole, which uses a combination of antibacterial agents such as tea tree oil and mugwort extract. However, this technology directly mixes the antibacterial agents into the polyurethane, failing to solve the problem of active ingredient volatilization during high-temperature processing. Patent CN113907486A discloses an antibacterial and deodorizing children's functional shoe, which uses mugwort composite fiber textile to form the middle layer. However, this technology relies on the antibacterial properties of the fiber itself, making it difficult to achieve stable retention of mugwort components in the foamed insole. Patent CN112914198A discloses a mugwort antibacterial and deodorizing sponge insole, which directly adds mugwort powder and mugwort essential oil to the sponge raw material. However, it does not effectively protect the volatile components of mugwort, resulting in significant losses during processing and use.

[0004] Therefore, how to effectively inhibit the high-temperature loss of volatile antibacterial components in Artemisia argyi extract during the preparation of polyurethane foam insoles, improve the retention rate of effective components of Artemisia argyi in the finished product, and enhance the antibacterial and deodorizing durability of the insoles is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention aims to provide an antibacterial and deodorizing foamed insole and its preparation method.

[0006] To achieve the above-mentioned objectives, the present invention adopts the following technical solution: An antibacterial and deodorizing foamed insole comprises the following raw materials: Artemisia argyi, aqueous ethanol solution, heat stabilizer, oil phase carrier, aqueous solution of sodium dodecyl sulfate, aqueous solution of methyl methacrylate resin, citric acid solution, Tween-80, fumed silica, polyether polyol, crosslinking agent, composite catalyst, organosilicon foam stabilizer, water, isocyanate.

[0007] The oil phase carrier is at least one of liquid paraffin and sucrose isobutyrate.

[0008] Preferably, the oil phase carrier is composed of liquid paraffin and sucrose isobutyrate in a mass ratio of 5-8:2-4.

[0009] The composite catalyst is prepared by compounding polyurethane foaming catalyst A33 and dibutyltin dilaurate in a mass ratio of 6-8:2-4.

[0010] The crosslinking agent is at least one of diethanolamine, pentaerythritol, sorbitol, triethanolamine, or glycerol.

[0011] The silicone foam stabilizer is selected from at least one of Niax L-580 and Dabco DC5950.

[0012] The isocyanate is at least one of polymethylene polyphenyl polyisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, or isophorone diisocyanate.

[0013] The heat-stabilizing carrier is at least one of hydroxypropyl-β-cyclodextrin, maltodextrin, polyvinylpyrrolidone, xanthan gum, α-tocopherol, and oxalic acid.

[0014] Preferably, the heat-stabilized carrier is composed of hydroxypropyl-β-cyclodextrin and polyvinylpyrrolidone in a mass ratio of 0.5-2:0.5-2.

[0015] The preparation method of the antibacterial and deodorizing foamed insole is as follows: Step 1: Extraction and concentration of active ingredients of Artemisia argyi: Crush and sieve the dried Artemisia argyi, mix the sieved material with an ethanol aqueous solution, heat and reflux to extract, filter, concentrate the filtrate under reduced pressure until the ethanol is completely evaporated to obtain Artemisia argyi extract, and store it in a refrigerator. Step 2, Preparation of Artemisia argyi modified biofunctional agent: Artemisia argyi extract was added to a heat-stable carrier, then water was added, and the mixture was stirred in a water bath to obtain a mixture; the mixture was dried, ground, and sieved to obtain a composite powder; the composite powder was mixed with an oil phase carrier as an oil phase core material, and added to an aqueous solution containing sodium dodecyl sulfate under high-speed shearing under heating conditions to emulsify and form an emulsion; an aqueous solution of methyl methacrylate resin was added dropwise to the emulsion, and the pH was adjusted to acidic, and the reaction was carried out by heating and stirring to allow the wall material to polymerize and deposit; after the reaction was completed, the mixture was cooled, centrifuged, washed, and dried to obtain Artemisia argyi microcapsules; the obtained Artemisia argyi microcapsules were mixed and dispersed with water, Tween-80, and fumed silica to obtain the Artemisia argyi modified biofunctional agent; Step 3: Preparation of Artemisia argyi functional polyol components: Based on polyether polyol, crosslinking agent, composite catalyst, organosilicon foam stabilizer, and water as chemical foaming agent are added in sequence and mixed evenly; then the biofunctional agent obtained in step 2 is added so that the Artemisia argyi microcapsule powder accounts for a specific proportion of the total mass of the polyol, and the mixture is mixed and degassed under vacuum conditions to obtain Artemisia argyi functional polyol components. Step 4, polyurethane foam molding and curing: The mugwort functional polyol component obtained in step 3 is mixed with isocyanate and then quickly poured into the insole mold. After it foams and gels, the foam-filled mold is transferred to a hot air drying tunnel for curing. After curing, the mold is demolded to obtain the antibacterial and deodorizing functional foamed insole.

[0016] Preferably, the preparation method of the antibacterial and deodorizing foamed insole is as follows: Step 1: Extraction and concentration of active ingredients from Artemisia argyi: Pulverize dried Artemisia argyi and pass it through a 20-80 mesh sieve. Take the sieve residue as raw material. Mix Artemisia argyi powder with an ethanol aqueous solution with a volume fraction of 50-80% at a material-to-liquid ratio of 1:10-20 g / mL. Reflux the mixture in a water bath at 60-80℃ for 1-3 times, 60-120 minutes each time. Combine the extracts and remove solid residues by hot filtration using a Buchner funnel. Collect the filtrate and concentrate it under reduced pressure at 50-70℃ and a vacuum degree of -0.07~-0.09MPa until all ethanol is removed to obtain Artemisia argyi extract. Seal and store at 1-5℃. The Artemisia argyi extract is a paste with a water content of ≤5%. Step 2, Preparation of Artemisia argyi modified biofunctional agent: Artemisia argyi extract and a heat-stabilized carrier are mixed at a mass ratio of 0.5-2:0.5-2, then water (15-25% of the total mass) is added. The mixture is stirred at 100-500 rpm for 10-20 minutes in a water bath at 30-50℃ to obtain a final mixture. The mixture is then transferred to a vacuum drying oven and dried at 30-50℃ at a temperature of -0.08 to -0.09. After drying at MPa for 6 hours, the product is ground and passed through an 80-200 mesh sieve to obtain a composite powder. The composite powder is mixed with an oil phase carrier to form the oil phase core material, with the oil phase carrier to Artemisia argyi extract at a mass ratio of 1:3-5. The oil phase core material is added to an aqueous solution containing 0.5-3% sodium dodecyl sulfate at a mass ratio of 1:3-5 (water bath at 40-60℃ and high-speed shearing at 6000-10000 rpm) and emulsified for 10-20 minutes to form a stable emulsion. A 40-60% aqueous solution of methyl methacrylated melamine resin is then added dropwise to the emulsion, with the oil phase carrier to Artemisia argyi extract at a mass ratio of 1:3-5. Simultaneously, 5-15% lemon juice is added. The pH of the acid solution was adjusted to 4-5, and the temperature was raised to 70-90℃ and stirred for 1-5 hours. After the reaction was completed, the mixture was cooled, centrifuged, washed with water 1-3 times, and dried in a vacuum drying oven at 80-90℃ for 5-15 hours to obtain Artemisia argyi microcapsules with an average particle size of 20-40μm. Water and Tween-80 were mixed at 100-300rpm for 3-8 minutes at 30-50℃. Then, a premixed dry powder of Artemisia argyi microcapsules and fumed silica was added. The mass ratio of Artemisia argyi microcapsules, water, Tween-80, and fumed silica was 40-60:40-50:2-4:1-3. The rotation speed was increased to 500-1000rpm and dispersed for 20-40 minutes to obtain the modified biofunctional agent of Artemisia argyi. Step 3, Preparation of Artemisia argyi functional polyol component: Based on polyether polyol, add the following components in the following order by mass percentage: 2-4% crosslinking agent, 1-1.5% composite catalyst, 0.5-2% organosilicon foam stabilizer, and 0.2-0.8% water as chemical foaming agent. Mix at 20-30℃ and 100-500 rpm for 3-8 minutes. Then add the biofunctional agent obtained in Step 2, with the amount added so that the Artemisia argyi microcapsule powder accounts for 4-6% of the total mass of the polyol. Mix and degas at a vacuum of -0.08~-0.095 MPa and 300-700 rpm for 10-30 minutes to obtain the Artemisia argyi functional polyol component. Step 4, Polyurethane Foaming and Curing: The Artemisia functional polyol component obtained in Step 3 is mixed with isocyanate at an isocyanate index of 1.05-1.1. The mixture is then mixed for 1-5 seconds at an injection pressure of 10-15 MPa using a high-pressure foaming machine to obtain a reaction mixture. The mixture is then quickly poured into an insole mold preheated to 50-70℃. After free foaming and gelling for 60-120 seconds, the foam-filled mold is directly transferred to a circulating hot air drying tunnel at 70-90℃ for curing for 10-50 minutes. After curing, the mold is removed and demolded to obtain the antibacterial and deodorizing functional foamed insole.

[0017] Observation showed that the structure of the Artemisia argyi microcapsule remained intact under the injection pressure and mixing time, with no obvious rupture.

[0018] Firstly, addressing the issue of significant loss of volatile antibacterial components from Artemisia argyi extract during high-temperature processing in the preparation of polyurethane foam insoles, this invention introduces a thermally stable carrier into the microcapsule oil phase core material. This thermally stable carrier effectively locks in the volatile oil molecules of Artemisia argyi through mechanisms such as molecular inclusion and glassy solidification, reducing their vapor pressure and thermal migration rate. This significantly improves the retention rate of the effective components of Artemisia argyi in subsequent high-temperature processes such as drying and curing, providing a material basis for the antibacterial and deodorizing functions of the insoles.

[0019] Secondly, addressing the issue that single thermally stabilized carriers have limited mechanisms of action and their protective effects still have room for improvement, this invention further combines a thermally stabilized carrier with molecular inclusion properties with a thermally stabilized carrier with hydrogen bonding properties. The two carriers work synergistically at both the molecular and aggregate scales; the former encapsulates individual volatile oil molecules, while the latter forms a three-dimensional network that solidifies the core material as a whole. Their complementary and synergistic effects further suppress the escape of volatile oils and improve the overall retention of the active ingredients in Artemisia argyi.

[0020] Finally, addressing the issue of low viscosity in the oil phase carrier and rapid diffusion of volatile oil molecules within it, this invention partially replaces conventional liquid paraffin with high-viscosity sucrose isobutyrate acetate. This compound, when combined with liquid paraffin, significantly increases the bulk viscosity of the oil phase core material, increases the diffusion resistance of volatile oil molecules, and slows their migration rate to the oil droplet surface. Thus, based on the synergistic combination with a heat-stabilized carrier, it further reduces the loss of Artemisia argyi volatile oil during high-temperature processing, allowing the final insole's antibacterial and deodorizing properties to be more fully realized.

[0021] Compared with the prior art, the present invention has the following beneficial technical effects: 1) This invention effectively inhibits the loss of volatile antibacterial components during high-temperature processing by pre-combining artemisia extract with a heat-stabilized carrier, and significantly improves the retention rate of effective components of artemisia in foamed insoles.

[0022] 2) This invention uses a thermally stable carrier that combines molecular inclusion and hydrogen bonding to lock in Artemisia argyi volatile oil at both the molecular and aggregate scales, which further improves the overall retention effect of Artemisia argyi active ingredients compared to a single carrier.

[0023] 3) By compounding high-viscosity sucrose isobutyrate in the oil phase carrier, this invention increases the diffusion resistance of volatile oil molecules and further reduces processing losses, thereby enabling the foamed insole to obtain better antibacterial and deodorizing properties. Detailed Implementation

[0024] Some material sources or parameters: Artemisia argyi: Originating in Nanyang, Henan Province, with a moisture content of ≤12% and a total volatile oil content of ≥0.8%. It is a commercially available raw material for processed Chinese medicinal herbs.

[0025] Methyl etherified hexamethyl hydroxymethyl melamine resin: Industrial grade methyl etherified melamine formaldehyde resin prepolymer, free formaldehyde ≤0.5%, viscosity at 25℃ 3000-5000 mPa·s.

[0026] Fumed silica: specific surface area 200±25 m² 2 / g, average primary particle size 12nm, SiO2 content ≥99.8%.

[0027] Polyether polyol: Grade: EP-330N, purchased from Shandong Lanxing Dongda Chemical Co., Ltd.

[0028] Polyurethane foaming catalyst A33: Industrial grade triethylenediamine / dipropylene glycol solution, triethylenediamine mass fraction 33%, moisture ≤0.5%, viscosity at 25℃ approximately 50 mPa·s.

[0029] Organosilicon foam stabilizer: Brand: Niax L-580, purchased from Momentive, USA.

[0030] Polymethylene polyphenyl polyisocyanate: Grade: PM-200, purchased from Wanhua Chemical.

[0031] Liquid paraffin: Cosmetic grade lightweight liquid paraffin, CAS: 8042-47-5, density at 20℃: 0.83-0.86 g / cm³ 3 Kinematic viscosity at 40℃ is 20-40 mm. 2 / s, purity ≥98%.

[0032] Sucrose isobutyrate: Food grade SAIB, CAS: 126-13-6, molecular weight approximately 846.9, acid value ≤0.2mgKOH / g, viscosity at 25℃ approximately 100,000 mPa·s, density 1.15 g / cm³ 3 .

[0033] Hydroxypropyl-β-cyclodextrin: pharmaceutical grade, CAS: 128446-35-5, degree of substitution 4-7, purity ≥98%, moisture ≤5%.

[0034] Maltodextrin: Food grade, CAS: 9050-36-6, DE value 15-20, moisture ≤6%, pH 4.5-6.5.

[0035] Polyvinylpyrrolidone: PVP K30, CAS: 9003-39-8, K value 27-33, purity ≥99%, moisture ≤5%.

[0036] Xanthan gum: food grade, CAS: 11138-66-2, 1% aqueous solution at 25℃ viscosity ≥1200 mPa·s, moisture ≤13%, 80 mesh powder.

[0037] α-Tocopherol: dl-α-Tocopherol, CAS: 10191-41-0, purity ≥96.0%.

[0038] Sagelic acid: a monomer from rosemary extract, CAS: 3650-09-7, purity ≥98% (HPLC).

[0039] All raw materials used in the embodiments of this invention are commercially available products.

[0040] Example 1

[0041] The preparation method of an antibacterial and deodorizing foamed insole is as follows, by weight: Step 1: Extraction and concentration of active ingredients from Artemisia argyi: Dry Artemisia argyi is pulverized and passed through a 40-mesh sieve. The sieve-passing material is used as raw material. Artemisia argyi powder is mixed with a 70% (v / v) ethanol aqueous solution at a material-to-liquid ratio of 1:15 g / mL. The mixture is refluxed twice in a 70°C water bath for 90 minutes each time. The two extracts are combined and hot filtered through a Buchner funnel to remove solid residue. The filtrate is collected and concentrated under reduced pressure at 60°C and -0.08 MPa until all ethanol is removed, yielding Artemisia argyi extract. The extract is sealed and stored at 4°C. The Artemisia argyi extract is a paste with a water content of ≤5%. Step 2, Preparation of Artemisia argyi modified biofunctional agent: Artemisia argyi extract and a heat-stabilized carrier were mixed at a mass ratio of 1:1, and then 20% of the total mass of deionized water was added. The mixture was stirred at 300 rpm for 15 minutes in a 40℃ water bath to obtain a mixture. The mixture was transferred to a vacuum drying oven and dried at 40℃ and -0.09 MPa for 6 hours. After drying, it was ground through a 100-mesh sieve to obtain a composite powder. The composite powder was mixed with an oil phase carrier as the oil phase core material, wherein the mass ratio of the oil phase carrier to the Artemisia argyi extract was 1:4. The mixture was then dried in a 50℃ water bath at 8000 rpm. Under high-speed shearing at rpm, the above-mentioned oil-phase core material was added to an aqueous solution containing 1.5% sodium dodecyl sulfate at an oil-to-water mass ratio of 1:4. Emulsification was carried out for 15 minutes to form a stable emulsion. A 50% aqueous solution of methyl methacrylated melamine resin was then added dropwise to the emulsion. The amount of resin added was 120% of the total mass of the oil-phase core material. Simultaneously, the pH was adjusted to 4.5 with a 10% citric acid solution. The mixture was heated to 80°C and stirred for 3 hours. After the reaction, the mixture was cooled, centrifuged, washed three times with deionized water, and dried in a vacuum drying oven at 85°C for 10 hours to obtain Artemisia argyi microcapsules with an average particle size of 30 μm. Deionized water and Tween-80 were then reacted at 40°C at a 200:1 ratio. Mix at rpm for 5 minutes, then add the premixed dry powder of Artemisia argyi microcapsules and fumed silica. The mass ratio of Artemisia argyi microcapsules, deionized water, Tween-80 and fumed silica is 50:45:3:2. Increase the speed to 800 rpm and disperse for 30 minutes to obtain the modified biofunctional agent of Artemisia argyi. Step 3: Preparation of Artemisia argyi functional polyol component: Based on polyether polyol EP-330N, the following components were added sequentially by mass percentage: 3% crosslinking agent glycerol, 1.2% composite catalyst, 1.0% organosilicon foam stabilizer, and 0.5% deionized water as chemical foaming agent. The composite catalyst was prepared by compounding polyurethane foaming catalyst A33 and dibutyltin dilaurate at a mass ratio of 7:3. The mixture was stirred at 25°C and 300 rpm for 5 minutes, and then the biofunctional agent prepared in Step 2 was added, with the amount added so that the Artemisia argyi microcapsule powder accounted for 5% of the total mass of the polyol. The mixture was stirred and degassed at a vacuum of -0.095 MPa and 500 rpm for 20 minutes to obtain the Artemisia argyi functional polyol component. Step 4, Polyurethane Foaming and Curing: The Artemisia functional polyol component obtained in Step 3 and polymethylene polyphenyl polyisocyanate are mixed at an isocyanate index of 1.08. The mixture is then mixed for 3 seconds at an injection pressure of 12 MPa using a high-pressure foaming machine to obtain a reaction mixture. The mixture is then quickly poured into an insole mold preheated to 60°C. After it has been allowed to bubble and gel freely for 90 seconds, the foam-filled mold is directly transferred to an 80°C circulating hot air drying tunnel for curing for 30 minutes. After curing, the mold is removed and demolded to obtain the antibacterial and deodorizing functional foamed insole.

[0042] The oil phase carrier is liquid paraffin.

[0043] The heat-stabilizing carrier is hydroxypropyl-β-cyclodextrin.

[0044] Example 2

[0045] The preparation method of an antibacterial and deodorizing foamed insole is basically the same as that in Example 1, except that the heat-stabilizing carrier is maltodextrin.

[0046] Example 3

[0047] The preparation method of an antibacterial and deodorizing foamed insole is basically the same as that in Example 1, except that the heat-stabilizing carrier is polyvinylpyrrolidone.

[0048] Example 4

[0049] The preparation method of an antibacterial and deodorizing foamed insole is basically the same as that in Example 1, except that the heat-stabilizing carrier is xanthan gum.

[0050] Example 5

[0051] The preparation method of an antibacterial and deodorizing foamed insole is basically the same as that in Example 1, except that the heat-stabilizing carrier is α-tocopherol.

[0052] Example 6

[0053] The preparation method of an antibacterial and deodorizing foamed insole is basically the same as that in Example 1, except that the heat-stabilizing carrier is sarsaparilla acid.

[0054] Example 7

[0055] The preparation method of an antibacterial and deodorizing foamed insole is basically the same as that in Example 1, except that the heat-stabilized carrier is composed of hydroxypropyl-β-cyclodextrin and polyvinylpyrrolidone in a mass ratio of 1:1.

[0056] Example 8

[0057] The preparation method of an antibacterial and deodorizing foamed insole is basically the same as that in Example 1, except that the heat-stabilizing carrier is composed of α-tocopherol and sarsaparilla acid in a mass ratio of 1:1.

[0058] Example 9

[0059] The preparation method of an antibacterial and deodorizing foamed insole is basically the same as that in Example 7, except that the oil phase carrier is composed of liquid paraffin and sucrose isobutyrate in a mass ratio of 7:3.

[0060] Comparative Example 1 A method for preparing an antibacterial and deodorizing foamed insole is as follows: Step 1: Extraction and concentration of active ingredients from Artemisia argyi: Dry Artemisia argyi is pulverized and passed through a 40-mesh sieve. The sieve-passing material is used as raw material. Artemisia argyi powder is mixed with a 70% (v / v) ethanol aqueous solution at a material-to-liquid ratio of 1:15 g / mL. The mixture is refluxed twice in a 70°C water bath for 90 minutes each time. The two extracts are combined and hot filtered through a Buchner funnel to remove solid residue. The filtrate is collected and concentrated under reduced pressure at 60°C and -0.08 MPa until all ethanol is removed, yielding Artemisia argyi extract. The extract is sealed and stored at 4°C. The Artemisia argyi extract is a paste with a water content of ≤5%. Step 2, Preparation of Artemisia argyi modified biofunctional agent: Artemisia argyi extract and oil phase carrier were mixed at a mass ratio of 4:1 as the oil phase core material, and the mixture was heated in a 50℃ water bath and at 8000℃. Under high-speed shearing at rpm, the above-mentioned oil-phase core material was added to an aqueous solution containing 1.5% sodium dodecyl sulfate at a mass ratio of 1:4 (oil:water). Emulsification was carried out for 15 minutes to form a stable emulsion. A 50% aqueous solution of methyl methacrylated melamine resin was then added dropwise to the emulsion. The amount of resin added was 120% of the total mass of the oil-phase core material. Simultaneously, the pH was adjusted to 4.5 with a 10% citric acid solution. The mixture was heated to 80°C and stirred for 3 hours. After the reaction, the mixture was cooled, centrifuged, washed three times with deionized water, and dried in a vacuum drying oven at 85°C for 10 hours to obtain Artemisia argyi microcapsules with an average particle size of 30 μm. First, deionized water and Tween-80 were mixed at 200 rpm for 5 minutes at 40°C. Then, a premixed dry powder of Artemisia argyi microcapsules and fumed silica was added. The mass ratio of Artemisia argyi microcapsules, deionized water, Tween-80, and fumed silica was 50:45:3:2. The rotation speed was increased to 800 rpm. Artemisia argyi modified biofunctional agent was prepared by dispersing at rpm for 30 minutes; Step 3: Preparation of Artemisia argyi functional polyol component: Based on polyether polyol EP-330N, the following components were added sequentially by mass percentage: 3% crosslinking agent glycerol, 1.2% composite catalyst, 1.0% organosilicon foam stabilizer, and 0.5% deionized water as chemical foaming agent. The composite catalyst was prepared by compounding polyurethane foaming catalyst A33 and dibutyltin dilaurate at a mass ratio of 7:3. The mixture was stirred at 25°C and 300 rpm for 5 minutes, and then the biofunctional agent prepared in Step 2 was added, with the amount added so that the Artemisia argyi microcapsule powder accounted for 5% of the total mass of the polyol. The mixture was stirred and degassed at a vacuum of -0.095 MPa and 500 rpm for 20 minutes to obtain the Artemisia argyi functional polyol component. Step 4, Polyurethane Foaming and Curing: The Artemisia functional polyol component obtained in Step 3 and polymethylene polyphenyl polyisocyanate are mixed at an isocyanate index of 1.08. The mixture is then mixed for 3 seconds at an injection pressure of 12 MPa using a high-pressure foaming machine to obtain a reaction mixture. The mixture is then quickly poured into an insole mold preheated to 60°C. After it has been allowed to bubble and gel freely for 90 seconds, the foam-filled mold is directly transferred to an 80°C circulating hot air drying tunnel for curing for 30 minutes. After curing, the mold is removed and demolded to obtain the antibacterial and deodorizing functional foamed insole.

[0061] The oil phase carrier is liquid paraffin.

[0062] Comparative Example 2 The preparation method of an antibacterial and deodorizing foamed insole is basically the same as that of Comparative Example 1, except that the Artemisia argyi extract is not added.

[0063] Test Example 1 Artemisia argyi characteristic component retention rate test: Take 5g of each of the foamed insole samples prepared in Examples 1-9 and Comparative Example 1, cut them into small pieces no larger than 5mm × 5mm × 5mm, place them in a 100mL stoppered conical flask, add 50mL of anhydrous ethanol, and extract at 40℃ with ultrasonic power of 200W for 30 minutes. Filter and collect the filtrate, and dilute to 100mL with anhydrous ethanol. The content of 1,8-cineole, a characteristic component of Artemisia argyi, in the filtrate was determined by gas chromatography-mass spectrometry (GC-MS). The chromatographic column was HP-5MS (30m × 0.25mm × 0.25μm), and the temperature program was as follows: initial temperature 60℃ for 2 minutes, then increased to 200℃ at 10℃ / min and held for 5 minutes. The carrier gas was high-purity helium, the flow rate was 1.0mL / min, the split ratio was 20:1, and the mass spectrometry was performed in selected ion monitoring mode (SIM, m / z 154, 108, 93). The 1,8-cineole standard was used for external standard quantification. The actual content of 1,8-cineole per gram of insole was calculated and compared with the theoretical addition amount (calculated based on the 1,8-cineole content in the Artemisia argyi extract in step 1). The retention rate (%) was calculated as (actual content / theoretical content) × 100%. The test results are shown in Table 1.

[0064] Table 1

[0065] Test Example 2 Antibacterial performance test: Referring to GB / T 20944.3-2008 "Evaluation of Antimicrobial Properties of Textiles - Part 3: Shaking Method", the polyurethane foam insole of Comparative Example 2 was used as the control sample. 3g of each of the foam insole samples prepared in Examples 1 and 2008 and Comparative Example 1 (cut into 5mm × 5mm pieces) were added to phosphate buffer containing a bacterial suspension of Staphylococcus aureus (ATCC 6538), with a bacterial concentration of 3 × 10⁻⁶. 5 CFU / mL, shaken at 24℃ and 150 rpm for 18 hours. The bacterial suspension before and after shaking was diluted and spread on nutrient agar plates, incubated at 37℃ for 24 hours, and the number of colonies was counted. The antibacterial rate (%) was calculated as follows: (number of viable bacteria in control sample - number of viable bacteria in test sample) / number of viable bacteria in control sample × 100%.

[0066] Each test was conducted 5 times, and the average value was taken. The relevant test data are summarized in Table 2.

[0067] Table 2

[0068] Examples 1 to 6 included the addition of a thermally stable carrier, while Comparative Example 1 did not include any thermally stable carrier. During high-temperature processing, volatile components in Artemisia argyi extract easily escape from the oil phase core material. The thermally stable carrier inhibits volatilization loss through mechanisms such as molecular inclusion, glassy solidification, hydrogen bonding networks, or anti-oxidation, thus its effect is superior to that of Comparative Example 1 without a thermally stable carrier. The hydroxypropyl-β-cyclodextrin used in Example 1 has a unique hydrophobic cavity structure, which can encapsulate small molecule components in Artemisia argyi volatile oil through molecular inclusion, directly reducing its vapor pressure. This physical locking mechanism is more efficient at inhibiting volatilization during production.

[0069] Example 7 uses both hydroxypropyl-β-cyclodextrin and polyvinylpyrrolidone as heat-stabilizing carriers, with complementary mechanisms of action. Hydroxypropyl-β-cyclodextrin encapsulates volatile oil molecules at the molecular scale, while polyvinylpyrrolidone forms a glassy network through hydrogen bonding to solidify the core material as a whole. Both act at the molecular and aggregate scales respectively, producing a synergistic effect. Therefore, Example 8 is superior to using Example 1 or Example 3 alone. Example 8 combines α-tocopherol and sarsaparilla acid, both phenolic antioxidants with the same mechanism of action—preventing oxidative degradation by capturing free radicals—but their contribution to inhibiting physical volatilization is limited, and their mechanisms overlap without complementarity, thus no synergistic effect is produced.

[0070] Example 9, based on Example 7, changed the oil phase carrier from pure liquid paraffin to a mixture of liquid paraffin and sucrose isobutyrate. Sucrose isobutyrate has extremely high bulk viscosity; when mixed with liquid paraffin, it significantly increased the overall viscosity of the oil phase core material, increased the diffusion resistance of Artemisia argyi volatile oil molecules in the oil phase, and slowed the rate of volatile oil migration to the oil droplet surface. This further reduced volatilization losses during high-temperature drying and aging. Therefore, Example 9 is superior to Example 7.

Claims

1. An antibacterial and deodorizing foamed insole, characterized in that, The raw materials include: Artemisia argyi, aqueous ethanol solution, heat stabilizer, oil phase carrier, aqueous solution of sodium dodecyl sulfate, aqueous solution of methyl methacrylate resin, citric acid solution, Tween-80, fumed silica, polyether polyol, crosslinking agent, composite catalyst, organosilicon foam stabilizer, water, and isocyanate. The heat-stabilizing carrier is at least one of hydroxypropyl-β-cyclodextrin, maltodextrin, polyvinylpyrrolidone, xanthan gum, α-tocopherol, and oxalic acid.

2. The antibacterial and deodorizing foamed insole as described in claim 1, characterized in that, The composite catalyst is prepared by compounding polyurethane foaming catalyst A33 and dibutyltin dilaurate in a mass ratio of 6-8:2-4.

3. The antibacterial and deodorizing foamed insole as described in claim 1, characterized in that, The crosslinking agent is at least one of diethanolamine, pentaerythritol, sorbitol, triethanolamine, or glycerol.

4. The antibacterial and deodorizing foamed insole as described in claim 1, characterized in that, The silicone foam stabilizer is selected from at least one of Niax L-580 and Dabco DC5950.

5. The antibacterial and deodorizing foamed insole as described in claim 1, characterized in that, The isocyanate is at least one of polymethylene polyphenyl polyisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, or isophorone diisocyanate.

6. The antibacterial and deodorizing foamed insole as described in claim 1, characterized in that, The oil phase carrier is at least one of liquid paraffin and sucrose isobutyrate.

7. The antibacterial and deodorizing foamed insole as described in claim 1, characterized in that, The oil phase carrier is composed of liquid paraffin and sucrose isobutyrate in a mass ratio of 5-8:2-4.

8. The antibacterial and deodorizing foamed insole as described in claim 1, characterized in that, The heat-stabilizing carrier is composed of hydroxypropyl-β-cyclodextrin and polyvinylpyrrolidone in a mass ratio of 0.5-2:0.5-2.

9. A method for preparing an antibacterial and deodorizing foamed insole as described in any one of claims 1-8, characterized in that, The method is as follows: Step 1: Extraction and concentration of active ingredients of Artemisia argyi: Crush and sieve the dried Artemisia argyi, mix the sieved material with an ethanol aqueous solution, heat and reflux to extract, filter, concentrate the filtrate under reduced pressure until the ethanol is completely evaporated to obtain Artemisia argyi extract, and store it in a refrigerator. Step 2, Preparation of Artemisia argyi modified biofunctional agent: Artemisia argyi extract was added to a heat-stable carrier, then water was added, and the mixture was stirred in a water bath to obtain a mixture; the mixture was dried, ground, and sieved to obtain a composite powder; the composite powder was mixed with an oil phase carrier as an oil phase core material, and added to an aqueous solution containing sodium dodecyl sulfate under high-speed shearing under heating conditions to emulsify and form an emulsion; an aqueous solution of methyl methacrylate resin was added dropwise to the emulsion, and the pH was adjusted to acidic, and the reaction was carried out by heating and stirring to allow the wall material to polymerize and deposit; after the reaction was completed, the mixture was cooled, centrifuged, washed, and dried to obtain Artemisia argyi microcapsules; the obtained Artemisia argyi microcapsules were mixed and dispersed with water, Tween-80, and fumed silica to obtain the Artemisia argyi modified biofunctional agent; Step 3: Preparation of Artemisia argyi functional polyol components: Based on polyether polyol, crosslinking agent, composite catalyst, organosilicon foam stabilizer, and water as chemical foaming agent are added in sequence and mixed evenly; then the biofunctional agent obtained in step 2 is added so that the Artemisia argyi microcapsule powder accounts for a specific proportion of the total mass of the polyol, and the mixture is mixed and degassed under vacuum conditions to obtain Artemisia argyi functional polyol components. Step 4, polyurethane foam molding and curing: The mugwort functional polyol component obtained in step 3 is mixed with isocyanate and then quickly poured into the insole mold. After it foams and gels, the foam-filled mold is transferred to a hot air drying tunnel for curing. After curing, the mold is demolded to obtain the antibacterial and deodorizing functional foamed insole.

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