Preparation method of antibacterial sleep-aiding latex pillow

Abstract

The invention discloses a preparation method of an antibacterial sleep-aiding latex pillow, and relates to the technical field of latex. Silicon dioxide is preliminarily modified through 4-trimethoxysilylbutyraldehyde, m-phenylenediamine-sodium sulfonate and triphosgene, the antibacterial and anti-dust effects can be achieved, then natural silk fibroin and collagen are used for further modification, performance is improved, meanwhile, the modified silicon dioxide can form a particle layer on the surface of natural latex, and the antibacterial and anti-dust effects are achieved. Modified silicon dioxide is used as a nucleating agent, and an interpenetrating network structure is formed through supercritical foaming, vulcanization, deblocking and crosslinking of the modified silicon dioxide and the nucleating agent, so that the mechanical property of the latex pillow is improved; according to the invention, after foaming, aromatic particles are doped, the sleep-aiding essential oil composition is fixedly loaded by using graphene aerogel microspheres, and cyclodextrin is used for encapsulation, so that the aromatic particles can release essential oil only when in use.

Description

Technical Field

[0001] The present invention relates to the technical field of latex, and specifically to a preparation method of an antibacterial and sleep - aiding latex pillow. Background Art

[0002] Regarding the manufacturing process of latex foaming materials or latex pillow cores, the current main process is to chemically foam natural latex. However, the odor contained in the chemical foaming agent affects the visual experience of using the latex pillow, and the natural latex after chemical foaming is prone to deformation and has insufficient support. With the continuous improvement of living standards, people are paying more and more attention to hygienic, safe, and healthy products, and functional latex products are becoming more and more popular among consumers. Due to the accelerating pace of life and relatively high life pressure nowadays, the number of people with poor sleep quality or even insomnia throughout the night is gradually increasing. Therefore, sleep - aiding pillows have emerged.

[0003] In addition, the pillow will show yellowish marks after being used for a long time. The main reasons for this phenomenon are as follows: dust is easily accumulated on the surface of the pillow, and the humidity, temperature, and sealing degree of the pillow are all conducive to the growth and reproduction of bacteria and fungi. Ordinary latex pillows do not have antibacterial and dust - proofing effects, and are extremely prone to yellowing during use. Moreover, long - term cleaning of the latex pillow will cause damage to its internal structure, shortening its lifespan and usage effect. Summary of the Invention

[0004] The purpose of the present invention is to provide an antibacterial and sleep - aiding latex pillow and its preparation method to solve the problems existing in the prior art.

[0005] To solve the above - mentioned technical problems, the present invention provides the following technical solution: An antibacterial and sleep - aiding latex pillow, comprising natural latex, modified silica, aromatic particles, vulcanizing agent, and gelling agent.

[0006] Further, the modified silica consists of 4 - trimethoxysilylbutyraldehyde, silica, m - phenylenediamine - 4 - sulfonic acid sodium salt, triphosgene, and a protein mixture; the protein mixture is natural silk fibroin and collagen.

[0007] Further, the aromatic particles are obtained by spraying an essential oil composition on graphene aerogel microcapsules and then encapsulating them with cyclodextrin; the essential oil composition is prepared by mixing tangerine peel essential oil, rose essential oil, lavender essential oil, and wild jujube seed oil.

[0008] Further, a preparation method of an antibacterial and sleep - aiding latex pillow includes the following preparation steps: (1)Mix pre-treated silica, sodium 4-sulfonatophenylenediamine, and absolute ethanol at a mass ratio of 0.15:0.2 - 0.4:15.8. After stirring at 100 - 200 rpm for 20 min, add 5 drops of glacial acetic acid. React at 65 - 72 °C for 1.5 - 2.0 h, then cool to room temperature, filter by suction, take the filter cake, wash it 3 times with ethanol, and dry it at 70 °C for 24 h to obtain Schiff base silica; (2)Mix solid phosgene particles and toluene at a mass ratio of 1:8. After stirring and dissolving, heat to 70 °C, and add a mixed solution of Schiff base silica that is 9.6 - 12.2 times the mass of the solid phosgene particles. The mass ratio of Schiff base silica to toluene in the mixed solution of Schiff base silica is 1:4. After ultrasonic dispersion at 400 - 600 W for 10 min, heat to 100 - 110 °C and keep the temperature for 1 - 3 h, then filter by suction and dry at 80 °C for 24 h to obtain a modified precursor; (3)At 45 °C, mix the modified precursor, triethylamine, and acetone at a mass ratio of 5 - 8:1.5:11 - 20. Stir at 500 - 700 rpm for 30 min, place it in an ice-water bath, cool for 10 min, add a protein aqueous solution that is 27 - 44 times the mass of the modified precursor. Stir at 5000 - 12000 rpm for 2 h, then heat to 15 °C and hydrate for 20 - 30 min. Then distill at a vacuum of -0.06 MPa and 40 °C for 1 - 3 h, and filter by suction to obtain modified silica; (4)Mix allyl-β-cyclodextrin, acrylic acid, 2,2'-azobisisobutyronitrile, and N,N-dimethylformamide at a mass ratio of 1:0.5:0.01:8. Under nitrogen protection, seal and react for 24 h to obtain a polymer solution. Open the seal, add aromatic microspheres that are 0.1 - 0.2 times the mass of the polymer solution. Stir at 400 - 600 rpm for 10 min, then seal and let it stand for 3 d. Place it in a Soxhlet extractor and extract with distilled water for 48 h. Place it in the refrigerator, pre-freeze for 24 h, then freeze at -50 °C for 3 - 4 h, and grind through a 100-mesh sieve to obtain aromatic particles; (5)Mix natural latex and modified silica at a mass ratio of 50:2 - 5. Under stirring at 200 - 400 rpm, add hydrochloric acid until the pH of the system is 2.7, then stop stirring. React at 60 °C for 3 - 5 h, and then add sulfur, potassium oleate, ricinoleic acid, coconut fatty acid, and aromatic particles at a mass ratio of 4 - 9:1 - 3:0.5 - 2:0.5 - 1:2 - 8. The mass ratio of sulfur to natural latex is 2 - 4:50. Stir at 10000 rpm for 10 - 20 min, then inject into a mold, evacuate and fill with carbon dioxide until the pressure is 10 - 14 MPa, foam at 70 - 80 °C for 1 - 3 h, and then cure in a steamer at 90 - 110 °C for 30 min and cool to obtain an antibacterial and sleep-aiding latex pillow.

[0009] Further, the preparation method of the pretreated silica in step (1) is as follows: Mix silica and absolute ethanol at a mass ratio of 1:23.7, disperse them by ultrasonic wave at 400 - 600W for 10 min, add an aqueous silane solution which is 10 - 18 times the mass of the silica. The mass ratio of 4-trimethoxysilylbutyraldehyde to deionized water in the aqueous silane solution is 1:2. After stirring evenly, react at 60 - 70 °C for 2 - 3 h, then wash with absolute ethanol and filter by suction until the filtrate is clear and transparent. Take the filter cake and dry it at 70 °C for 24 h.

[0010] Further, the particle size of the silica is 60 - 100 μm.

[0011] Further, the mass ratio of natural silk fibroin, collagen, and ice water in the protein aqueous solution in step (3) is 3:1:55.

[0012] Further, the preparation method of the aromatic microspheres in step (4) is as follows: Spray a plant essential oil composition which is 0.05 - 0.2 times the mass of the graphene aerogel microspheres on the graphene aerogel microspheres. Spray it in 3 times. After each spraying, place it in the refrigerator and freeze for 30 - 60 min, then tumble the graphene aerogel microspheres once and continue spraying. After the spraying is completed, place it in the refrigerator and freeze for 24 h.

[0013] Further, the mass ratio of tangerine peel essential oil, rose essential oil, lavender essential oil, and wild jujube seed oil in the plant essential oil composition is 0.3 - 1:1:1:0.1 - 0.4.

[0014] Further, the particle size of the graphene aerogel microspheres is 50 - 100 μm.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: The present invention uses natural latex, modified silica, and aromatic particles as the main raw materials, with the help of modified silica as a nucleating agent, and obtains a latex pillow through supercritical foaming to achieve the effects of antibacterial, anti-dust adhesion, sleep aid, and anti-allergy.

[0016] First, the present invention adopts the silicon oxygen bond of 4-trimethoxysilyl butyraldehyde to be grafted on the surface of silica, and then, the aldehyde group is used to react with the amino group of sodium m-phenylenediamine-4-sulfonate to form a Schiff base antibacterial group, which effectively inhibits the growth of bacteria; then, the remaining unreacted amino group reacts with solid phosgene to introduce isocyanate groups, so that it can react with the amino group, hydroxyl group and other active groups of silk fibroin and collagen, and then the protein is grafted on the surface of silica. Since silk fibroin and collagen have excellent biocompatibility, they can promote the compatibility of modified silica with natural rubber, reduce the defects between chains, and strengthen the performance of latex molecular chains. In addition, silk fibroin and collagen contain a large number of hydrophilic groups, which can adsorb the hydrophilic groups in the environment. Trace amounts of moisture form a molecular conductive layer, which improves antistatic properties and prevents the adsorption of charged dust. The side chain is connected to a sulfonic acid group-metal ion bond, which can decomplex to generate positive and negative ions for ionic conductivity, thereby improving the ability to prevent dust from being contaminated. At the same time, silk fibroin has certain antibacterial properties and can work together with Schiff base to improve the antibacterial ability of latex pillows. Then, the modified silica relies on the protein mixture in the molecular chain to coagulate with natural latex, and wraps the modified silica particle layer on the surface of the natural latex particles. During the vulcanization and foaming process, the two are unsealed and then cross-linked to form an interpenetrating network structure, which improves the mechanical properties of the latex pillow. At the same time, the introduction of silk fibroin and collagen greatly reduces the allergic nature of natural latex.

[0017] Secondly, tangerine peel essential oil can achieve a calming effect, rose essential oil has the effects of regulating qi and relieving depression, and can effectively relieve insomnia, lavender has a calming and tranquilizing effect, and Chinese jujube seed oil has a calming and hypnotic effect. These essential oils are mixed, sprayed on graphene aerogel microspheres, and penetrate into the microspheres along the pores. The essential oil components all contain unsaturated double bonds, which can form π-π conjugation with the unsaturated double bonds on graphene, thereby fixing the essential oil in the graphene and achieving a sustained release effect. Cyclodextrin is then used to encapsulate the microspheres to prevent the aromatic particles from being released in the natural environment. When in use, the cyclodextrin is subjected to external pressure, which reduces the inclusion effect, allowing the essential oil to be released, which promotes the user's sleep. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0019] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the test methods of the various indicators of the antibacterial sleep-aiding latex pillow prepared in the following examples are as follows: Antibacterial: For the examples and comparative examples of the same size, the antibacterial rate was tested with reference to GB / T 20944.3.

[0020] Sleep aid: Tested using the Pittsburgh Sleep Quality Index (PSQI). 70 test subjects were selected and divided into 7 groups of 10 people each, randomly including both men and women, aged 20 - 60 years. After 3 months of use, the average value was taken for the test.

[0021] Anti - dust adhesion: Examples and comparative examples of the same mass were placed in a connected air duct system. Standard dust simulating real atmospheric dust was regularly added to the air duct system. 20 g of standard dust was added to the air duct system every 2 h. The fan ran for 10 minutes and then stopped for 10 minutes, which was regarded as a cycle. The blowing speed of dust was 1 - 2 m / s, and it lasted for 2 days. The anti - dust adhesion effect was measured, and the larger the value of the anti - dust adhesion effect, the better. Anti - dust adhesion effect = (weight of the latex pillow after dust adhesion treatment - weight of the latex pillow before dust adhesion treatment) / weight of the latex pillow before dust adhesion treatment × 100%.

[0022] Mechanical properties: Examples and comparative examples of the same size were tested with reference to Method A in GB / T 6669. The test temperature was 70 °C, the test time was 22 h, and the compression was 75%; the rebound rate was tested with reference to GB / T 6670.

[0023] Example 1 (1) Silicon dioxide with a particle size of 60 μm and absolute ethanol were mixed at a mass ratio of 1:23.7, ultrasonically dispersed for 10 min at 400 W, and an aqueous silane solution 10 times the mass of the silicon dioxide was added. The mass ratio of 4 - trimethoxysilylbutyraldehyde to deionized water in the aqueous silane solution was 1:2. After stirring evenly, the reaction was carried out at 60 °C for 2 h, then washed with absolute ethanol and filtered by suction until the filtrate was clear and transparent. The filter cake was taken and dried at 70 °C for 24 h to obtain pretreated silicon dioxide. (2) Pretreated silicon dioxide, m - phenylenediamine - 4 - sulfonic acid sodium salt, and absolute ethanol were mixed at a mass ratio of 0.15:0.2:15.8, stirred at 100 rpm for 20 min, then 5 drops of glacial acetic acid were added, and the reaction was carried out at 65 °C for 1.5 h. After cooling to room temperature, it was filtered by suction. The filter cake was taken, washed 3 times with ethanol, and dried at 70 °C for 24 h to obtain Schiff base silicon dioxide. (3) Solid phosgene particles and toluene were mixed at a mass ratio of 1:8. After stirring and dissolving, the temperature was raised to 70 °C, and a Schiff base silicon dioxide mixture 9.6 times the mass of the solid phosgene particles was added. The mass ratio of Schiff base silicon dioxide to toluene in the Schiff base silicon dioxide mixture was 1:4. After ultrasonically dispersing at 400 W for 10 min, the temperature was raised to 100 °C, and the reaction was carried out at this temperature for 1 h. Then it was filtered by suction and dried at 80 °C for 24 h to obtain a modified precursor. (4)At 45 °C, mix the modified precursor, triethylamine, and acetone in a mass ratio of 5:1.5:11, stir at 500 rpm for 30 min, place in an ice-water bath, cool for 10 min, add a protein aqueous solution 27 times the mass of the modified precursor. The mass ratio of natural silk fibroin, collagen, and ice water in the protein aqueous solution is 3:1:55. After stirring at 5000 rpm for 2 h, raise the temperature to 15 °C, hydrate for 20 min, then distill at a vacuum of -0.06 MPa and 40 °C for 1 h, and filter to obtain modified silica; (5)Mix orange peel essential oil, rose essential oil, lavender essential oil, and wild jujube seed oil in a mass ratio of 0.3:1:1:0.1, stir evenly to obtain a plant essential oil composition. Spray a plant essential oil composition 0.05 times the mass of the graphene aerogel microspheres with a particle size of 50 μm on the graphene aerogel microspheres. Spray in 3 times. After each spraying, place in the refrigerator and freeze for 30 min, then roll the graphene aerogel microspheres once and continue spraying. After spraying is completed, place in the refrigerator and freeze for 24 h to obtain aromatic microspheres; (6)Mix allyl-β-cyclodextrin, acrylic acid, 2,2'-azobisisobutyronitrile, and N,N-dimethylformamide in a mass ratio of 1:0.5:0.01:8. Under nitrogen protection, seal and react for 24 h to obtain a polymer solution. Open the seal, add aromatic microspheres 0.1 times the mass of the polymer solution, stir at 400 rpm for 10 min, then seal and place for 3 d, then place in a Soxhlet extractor and extract with distilled water for 48 h. Place in the refrigerator, pre-freeze for 24 h, then freeze at -50 °C for 3 h, and grind through a 100-mesh sieve to obtain aromatic particles; (7)Mix natural latex and modified silica in a mass ratio of 50:2. Under stirring at 200 rpm, add hydrochloric acid until the pH of the system is 2.7, then stop stirring. React at 60 °C for 3 h, then add sulfur, potassium oleate, ricinoleic acid, coconut fatty acid, and aromatic particles in a mass ratio of 4:1:0.5:0.5:2. The mass ratio of sulfur to natural latex is 2:50. After stirring at 10000 rpm for 10 min, inject into a mold, evacuate and fill with carbon dioxide until the pressure is 10 MPa, foam at 70 °C for 1 h, then place in a steamer at 90 °C and vulcanize for 30 min, and cool to obtain an antibacterial and sleep-aiding latex pillow.

[0024] Example 2 (1)Mix silica with a particle size of 80 μm and absolute ethanol in a mass ratio of 1:23.7, ultrasonically disperse at 50 W for 10 min, add an aqueous silane solution 14 times the mass of the silica. The mass ratio of 4-trimethoxysilylbutyraldehyde to deionized water in the aqueous silane solution is 1:2. After stirring evenly, react at 65 °C for 2.5 h, then wash with absolute ethanol and filter until the filtrate is clear and transparent. Take the filter cake and dry at 70 °C for 24 h to obtain pretreated silica; (2) Mix the pretreated silica, sodium 4-sulfonatophenylenediamine, and absolute ethanol at a mass ratio of 0.15:0.3:15.8. After stirring at 150 rpm for 20 min, add 5 drops of glacial acetic acid. After reacting at 65 - 72 °C for 1.8 h, cool to room temperature, perform suction filtration, take the filter cake, wash it 3 times with ethanol, and dry it at 70 °C for 24 h to obtain Schiff base silica; (3) Mix the solid phosgene particles and toluene at a mass ratio of 1:8. After stirring and dissolving, heat to 70 °C, and add a mixed solution of Schiff base silica that is 10.9 times the mass of the solid phosgene particles. The mass ratio of Schiff base silica to toluene in the mixed solution of Schiff base silica is 1:4. After ultrasonic dispersion at 500 W for 10 min, heat to 105 °C and keep the temperature for reaction for 2 h. Then perform suction filtration and dry at 80 °C for 24 h to obtain a modified precursor; (4) At 45 °C, mix the modified precursor, triethylamine, and acetone at a mass ratio of 6.5:1.5:15.5. Stir at 600 rpm for 30 min, place it in an ice-water bath, cool for 10 min, and add a protein aqueous solution that is 35.5 times the mass of the modified precursor. The mass ratio of natural silk fibroin, collagen, and ice water in the protein aqueous solution is 3:1:55. After stirring at 8500 rpm for 2 h, heat to 15 °C and hydrate for 25 min. Then distill at a vacuum degree of -0.06 MPa and 40 °C for 2 h, and perform suction filtration to obtain modified silica; (5) Mix orange peel essential oil, rose essential oil, lavender essential oil, and wild jujube seed oil at a mass ratio of 0.65:1:1:0.25, and stir evenly to obtain a plant essential oil composition. Spray the plant essential oil composition that is 0.13 times the mass of the graphene aerogel microspheres with a particle size of 75 μm on the graphene aerogel microspheres. Spray in 3 times. After each spraying, place it in the refrigerator and freeze for 45 min, then tumble the graphene aerogel microspheres once and continue spraying. After spraying is completed, place it in the refrigerator and freeze for 24 h to obtain aromatic microspheres; (6) Mix allyl-β-cyclodextrin, acrylic acid, 2,2'-azobisisobutyronitrile, and N,N-dimethylformamide at a mass ratio of 1:0.5:0.01:8. Under nitrogen protection, seal and react for 24 h to obtain a polymer solution. Open the seal, add aromatic microspheres that are 0.15 times the mass of the polymer solution. After stirring at 500 rpm for 10 min, seal and let it stand for 3 d. Then place it in a Soxhlet extractor and extract with distilled water for 48 h. Place it in the refrigerator, pre-freeze for 24 h, then freeze at -50 °C for 3.5 h, and grind through a 100-mesh sieve to obtain aromatic particles; (7) Mix natural latex and modified silica in a mass ratio of 50:3.5. While stirring at 300 rpm, add hydrochloric acid until the pH of the system reaches 2.7, then stop stirring. After reacting at 60 °C for 4 h, add sulfur, potassium oleate, ricinoleic acid, coconut fatty acid, and aromatic particles in a mass ratio of 6.5:2:1.3:0.7:5. The mass ratio of sulfur to natural latex is 3:50. After stirring at 10000 rpm for 15 min, inject it into a mold, evacuate and fill it with carbon dioxide until the pressure reaches 12 MPa, foam at 75 °C for 2 h, then place it in a steam box at 100 °C for vulcanization for 30 min, and cool to obtain an antibacterial and sleep-aiding latex pillow.

[0025] Example 3 (1) Mix silica with a particle size of 100 μm and absolute ethanol in a mass ratio of 1:23.7, disperse it by ultrasonic wave at 600 W for 10 min, add an aqueous silane solution 18 times the mass of silica. The mass ratio of 4-trimethoxysilylbutyraldehyde to deionized water in the aqueous silane solution is 1:2. After stirring evenly, react at 70 °C for 3 h, then wash with absolute ethanol and filter by suction until the filtrate is clear and transparent. Take the filter cake and dry it at 70 °C for 24 h to obtain pretreated silica. (2) Mix pretreated silica, m-phenylenediamine-4-sulfonate, and absolute ethanol in a mass ratio of 0.15:0.4:15.8, stir at 200 rpm for 20 min, then drop in 5 drops of glacial acetic acid. After reacting at 72 °C for 2 h, cool to room temperature, filter by suction, take the filter cake, wash it with ethanol 3 times, and dry it at 70 °C for 24 h to obtain Schiff base silica. (3) Mix solid phosgene particles and toluene in a mass ratio of 1:8, stir and dissolve, then heat up to 70 °C, add a mixed solution of Schiff base silica 12.2 times the mass of solid phosgene particles. The mass ratio of Schiff base silica to toluene in the mixed solution of Schiff base silica is 1:4. After ultrasonic dispersion at 600 W for 10 min, heat up to 110 °C and keep the temperature for reaction for 3 h, then filter by suction and dry at 80 °C for 24 h to obtain a modified precursor. (4) At 45 °C, mix the modified precursor, triethylamine, and acetone in a mass ratio of 8:1.5:20, stir at 700 rpm for 30 min, place it in an ice-water bath, cool for 10 min, add a protein aqueous solution 44 times the mass of the modified precursor. The mass ratio of natural silk fibroin, collagen, and ice water in the protein aqueous solution is 3:1:55. After stirring at 12000 rpm for 2 h, heat up to 15 °C and hydrate for 30 min, then distill at a vacuum degree of -0.06 MPa and 40 °C for 3 h, and filter by suction to obtain modified silica. (5) Mix orange peel essential oil, rose essential oil, lavender essential oil, and wild jujube seed oil in a mass ratio of 1:1:1:0.4, stir evenly to obtain a plant essential oil composition. Spray the plant essential oil composition 0.2 times the mass of the graphene aerogel microspheres on the graphene aerogel microspheres with a particle size of 100 μm. Spray in 3 times. After each spraying, place it in the refrigerator and freeze for 60 min. Then, tumble the graphene aerogel microspheres once and continue spraying. After spraying is completed, place it in the refrigerator and freeze for 24 h to obtain aromatic microspheres; (6) Mix allyl-β-cyclodextrin, acrylic acid, 2,2'-azobisisobutyronitrile, and N,N-dimethylformamide in a mass ratio of 1:0.5:0.01:8. Under nitrogen protection, seal and react for 24 h to obtain a polymer solution. Open it, add aromatic microspheres 0.2 times the mass of the polymer solution. After stirring at 600 rpm for 10 min, seal and place for 3 d. Then, place it in a Soxhlet extractor and extract with distilled water for 48 h. Place it in the refrigerator, pre-freeze for 24 h, then freeze at -50 °C for 4 h, and grind through a 100-mesh sieve to obtain aromatic particles; (7) Mix natural latex and modified silica in a mass ratio of 50:5. Under stirring at 400 rpm, add hydrochloric acid until the pH of the system is 2.7, then stop stirring. React at 60 °C for 5 h. Then, add sulfur, potassium oleate, ricinoleic acid, coconut oil acid, and aromatic particles in a mass ratio of 9:3:2:1:8. The mass ratio of sulfur to natural latex is 4:50. After stirring at 10000 rpm for 20 min, inject it into a mold, evacuate and fill with carbon dioxide until the pressure is 14 MPa, foam at 80 °C for 3 h, and then cure in a steam box at 110 °C for 30 min and cool to obtain an antibacterial and sleep-aiding latex pillow.

[0026] Comparative Example 1 The difference between Comparative Example 1 and Example 2 is that steps (1) to (4) are absent. Step (7) is changed to: Mix natural latex and silica in a mass ratio of 50:3.5. Under stirring at 300 rpm, add hydrochloric acid until the pH of the system is 2.7, then stop stirring. React at 60 °C for 4 h. Then, add sulfur, potassium oleate, ricinoleic acid, coconut oil acid, and aromatic particles in a mass ratio of 6.5:2:1.3:0.7:5. The mass ratio of sulfur to natural latex is 3:50. After stirring at 10000 rpm for 15 min, inject it into a mold, evacuate and fill with carbon dioxide until the pressure is 12 MPa, foam at 75 °C for 2 h, and then cure in a steam box at 100 °C for 30 min and cool to obtain an antibacterial and sleep-aiding latex pillow. The remaining steps are the same as those in Example 2.

[0027] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is that step (2) is absent, and step (3) is changed to: Mix solid phosgene particles and toluene at a mass ratio of 1:8, stir to dissolve, then heat up to 70°C, add a pre-treated silica mixed solution that is 10.9 times the mass of the solid phosgene particles. The mass ratio of pre-treated silica to toluene in the pre-treated silica mixed solution is 1:4. After ultrasonic dispersion at 500W for 10 min, heat up to 105°C, keep the temperature for reaction for 2 h, then perform suction filtration, and dry at 80°C for 24 h to obtain a modified precursor. The remaining steps are the same as those in Example 2.

[0028] Comparative Example 3 The difference between Comparative Example 3 and Example 2 is that step (3) is absent, and step (4) is changed to: At 45°C, mix Schiff base silica, triethylamine, and acetone at a mass ratio of 6.5:1.5:15.5, stir at 600 rpm for 30 min, place in an ice-water bath, cool for 10 min, add a protein aqueous solution that is 35.5 times the mass of the Schiff base silica. The mass ratio of natural silk fibroin, collagen, and ice water in the protein aqueous solution is 3:1:55. After stirring at 8500 rpm for 2 h, heat up to 15°C, hydrate for 25 min, then distill at a vacuum degree of -0.06 MPa and 40°C for 2 h, and then perform suction filtration to obtain modified silica. The remaining steps are the same as those in Example 2.

[0029] Comparative Example 4 The difference between Comparative Example 4 and Example 2 is that step (6) is absent, and step (7) is changed to: Mix natural latex and modified silica at a mass ratio of 50:3.5, under stirring at 300 rpm, add hydrochloric acid until the pH of the system is 2.7, then stop stirring. After reacting at 60°C for 4 h, add sulfur, potassium oleate, ricinoleic acid, coconut fatty acid, and aromatic microspheres at a mass ratio of 6.5:2:1.3:0.7:5. The mass ratio of sulfur to natural latex is 3:50. After stirring at 10000 rpm for 15 min, inject into a mold, evacuate and fill with carbon dioxide until the pressure is 12 MPa, foam at 75°C for 2 h, then place in a steamer at 100°C for vulcanization for 30 min, and cool to obtain an antibacterial and sleep-aiding latex pillow. The remaining steps are the same as those in Example 2.

[0030] Comparative Example 5 The difference between Comparative Example 5 and Example 2 is that step (5) is absent, and step (6) is changed to: Dissolve β-cyclodextrin in distilled water that is 50 times the mass of β-cyclodextrin, add a plant essential oil composition at a wall-core ratio of 3:1. The mass ratio of tangerine peel essential oil, rose essential oil, lavender essential oil, and wild jujube seed oil in the plant essential oil composition is 0.3:1:1:0.1. After stirring at 40°C and 400 rpm for 3 h, let it stand for precipitation for 12 h, perform suction filtration, and dry at 60°C for 5 h to obtain aromatic particles.

[0031] Effect Example Table 1 below shows the performance analysis results of the antibacterial sleep-aiding latex pillows of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0032] Table 1 From the comparison of the rebound test data of the embodiment and the comparative example, it can be found that the modified silica used in the present invention can wrap the natural latex particles. During the vulcanization and foaming process, the two are unsealed and then cross-linked to form an interpenetrating network structure, thereby improving the mechanical properties of the latex pillow; from the comparison of the antibacterial rate experimental data of the embodiment and the comparative example, it can be found that the present invention uses 4-trimethoxysilylbutyraldehyde, sodium m-phenylenediamine-4-sulfonate and protein mixture as raw materials to modify silica, so that Schiff base and silk protein are introduced into its surface, which work together to improve the antibacterial ability of the latex pillow; from the comparison of the sleep aid and usage time experimental data of the embodiment and the comparative example, it can be found that the tangerine peel essential oil, rose essential oil, lavender essential oil, acid essential oil used in the present invention Jujube seed oil has an excellent sleep-inducing effect. At the same time, graphene aerogel microspheres can play a fixing role and enhance the sustained-release effect. At the same time, cyclodextrin encapsulation can prevent the essential oil from volatilizing at high temperature during the vulcanization process, thereby improving the sleep-inducing and sustained-release effects. From the comparison of the anti-dust and resistivity experimental data of the embodiment and the comparative example, it can be found that the present invention introduces a sulfonic acid group-metal ion bond on the surface of silica, which can decomplex and generate positive and negative ions for ion conduction, thereby improving the anti-dust ability. At the same time, silk protein and collagen contain a large number of hydrophilic groups, which can improve the hydrophilicity of natural latex, effectively adsorb trace moisture in the environment, form a molecular conductive layer, improve antistatic properties, and prevent the adsorption of charged dust.

[0033] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A method for preparing an antibacterial sleep-aiding latex pillow, characterized in that: The method comprises the following preparation steps: (1) Silica with a particle size of 80 μm and anhydrous ethanol were mixed in a mass ratio of 1:23.7, and ultrasonically dispersed at 50 W for 10 min. A silane aqueous solution with a mass ratio of 14 times that of the silica was added, and the mass ratio of 4-trimethoxysilylbutyraldehyde to deionized water in the silane aqueous solution was 1:

2. After stirring evenly, the mixture was reacted at 65 ° C for 2.5 h, washed with anhydrous ethanol, filtered until the filtrate was clear and transparent, and the filter cake was taken and dried at 70 ° C for 24 h to obtain pretreated silica; (2) Pretreated silica, sodium m-phenylenediamine-4-sulfonate, and anhydrous ethanol were mixed in a mass ratio of 0.15:0.3:15.8, stirred at 150 rpm for 20 min, and then 5 drops of glacial acetic acid were added. The mixture was reacted at 65-72 °C for 1.8 h, cooled to room temperature, filtered, and the filter cake was washed with ethanol for 3 times, and dried at 70 °C for 24 h to obtain Schiff base silica; (3) Mix solid phosgene particles and toluene in a mass ratio of 1:8, stir and dissolve, heat to 70°C, add a Schiff base silica mixed solution of 10.9 times the mass of the solid phosgene particles, and the mass ratio of Schiff base silica to toluene in the Schiff base silica mixed solution is 1:

4. After 500W ultrasonic dispersion for 10 minutes, heat to 105°C, keep warm for reaction for 2 hours, filter, and dry at 80°C for 24 hours to obtain a modified precursor; (4) At 45°C, the modified precursor, triethylamine and acetone were mixed in a mass ratio of 6.5:1.5:15.5, stirred at 600 rpm for 30 min, placed in an ice water bath, cooled for 10 min, and a protein aqueous solution 35.5 times the mass of the modified precursor was added. The mass ratio of natural silk fibroin, collagen and ice water in the protein aqueous solution was 3:1:

55. After stirring at 8500 rpm for 2 h, the mixture was heated to 15°C and hydrated for 25 min. After distillation at a vacuum degree of -0.06 MPa and 40°C for 2 h, the modified silica was obtained by suction filtration. (5) Tangerine peel essential oil, rose essential oil, lavender essential oil, and Chinese date seed oil are mixed in a mass ratio of 0.65:1:1:0.25, and stirred evenly to obtain a plant essential oil composition, and the plant essential oil composition in an amount of 0.13 times the mass of the graphene aerogel microspheres is sprayed onto graphene aerogel microspheres with a particle size of 75 μm, and the spraying is divided into 3 times. After each spraying, the graphene aerogel microspheres are placed in a refrigerator and frozen for 45 minutes. The graphene aerogel microspheres are rolled once and then sprayed again. After the spraying is completed, the graphene aerogel microspheres are placed in a refrigerator and frozen for 24 hours to obtain aromatic microspheres; (6) Allyl-β-cyclodextrin, acrylic acid, 2,2'-azobisisobutyronitrile, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.5:0.01:8, sealed and reacted for 24 hours under nitrogen protection to obtain a polymer solution, opened the seal, and added with aromatic microspheres 0.15 times the mass of the polymer solution, stirred at 500 rpm for 10 minutes, sealed and left for 3 days, placed in a Soxhlet extractor and extracted with distilled water for 48 hours, placed in a refrigerator, pre-frozen for 24 hours, and then frozen at -50°C for 3.5 hours, and ground through a 100-mesh sieve to obtain aromatic particles; (7) Natural latex and modified silica were mixed in a mass ratio of 50:3.

5. Under stirring at 300 rpm, hydrochloric acid was added until the pH value of the system was 2.

7. Then, stirring was stopped. After reacting at 60°C for 4 hours, sulfur, potassium oleate, ricinoleic acid, coconut acid and aromatic particles were added in a mass ratio of 6.5:2:1.3:0.7:

5. The mass ratio of sulfur to natural latex was 3:

50. After stirring at 10,000 rpm for 15 minutes, the mixture was injected into a mold. The mixture was evacuated and filled with carbon dioxide to a pressure of 12 MPa. After foaming at 75°C for 2 hours, the mixture was placed in a steamer at 100°C for vulcanization for 30 minutes. The mixture was cooled to obtain an antibacterial sleep-aiding latex pillow.

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