Antibacterial plastic inner bag material and preparation method thereof
By preparing a resistant plastic inner bag material that combines nanoparticle composite photocatalysts with antibacterial agents, the problems of easy bacterial growth and narrow photodegradation range of plastic inner bags were solved, achieving both antibacterial and rapid photodegradation effects.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- 北京金博轩科技发展有限公司
- Filing Date
- 2023-05-09
- Publication Date
- 2026-04-21
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Existing plastic inner bags are prone to bacterial growth, which cannot guarantee the proper storage of items. Furthermore, the application range of traditional photodegradable plastics is narrow and cannot meet the wide range of needs.
By combining nanoparticle composite photocatalysts with antibacterial agents, antibacterial plastic inner bag materials are prepared through irradiation and multiple extrusion blown film processes. This forms a porous structure to improve photodegradation performance, while the antibacterial agent inhibits bacterial growth.
It achieves antibacterial properties and rapid photodegradation of plastic inner bags, expands the application range of photodegradable plastics, and improves material performance and degradation efficiency.
Smart Images
Figure BDA0004219369890000131
Abstract
Description
Technical Field
[0001] This invention relates to the field of plastics technology, specifically to a resistant plastic inner bag material and its preparation method. Background Technology
[0002] Plastic inner bags, made primarily of plastic, are essential items in daily life, commonly used to store other goods. They are widely used due to their low cost, light weight, large capacity, and ease of storage. However, their extremely long degradation cycle and difficult disposal have led some countries to ban their production and use. Currently, with the growing demand for low-carbon living, traditional plastics are gradually fading from the market, giving rise to biodegradable plastic materials. Photodegradable plastic technology matured in the 1980s, and its production has grown rapidly. However, its application is limited to areas with long hours of sunshine and abundant sunlight, restricting its use to areas like agricultural mulch. Furthermore, plastic inner bags are prone to bacterial growth, failing to guarantee the proper storage of items. Summary of the Invention
[0003] The purpose of this invention is to provide a resistant plastic inner bag material and its preparation method to solve the problems existing in the prior art.
[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a resistant plastic inner bag material, wherein the resistant plastic inner bag material is obtained by co-extrusion of nanoparticles, polyethylene, and maleic anhydride-grafted polyethylene, followed by irradiation, and then secondary extrusion and blown film preparation with additives.
[0005] Furthermore, the nanoparticles are prepared by mixing epoxy resin E-51, antibacterial agent, and solvent, adding carboxylated composite photocatalyst, ultrasonically dispersing evenly, reacting in a water bath for a period of time, and then drying by alternating hot and cold temperatures.
[0006] Furthermore, the composite photocatalyst is prepared by combining layered tungsten disulfide with titanium dioxide precursor sol, drying to form aerogel-encapsulated titanium / tungsten particles, and then calcining them together with urea to deposit metallic palladium.
[0007] Furthermore, the antibacterial agent is prepared from 4-bromo-3-mercaptobenzoic acid, 4-(hydroxymethyl)-3-vinylacetophenone, and hydrazine hydrate.
[0008] Furthermore, a method for preparing a resistant plastic inner bag material includes the following preparation steps:
[0009] (1) Mix tetrabutyl titanate and anhydrous ethanol at a mass ratio of 1:1.44 and stir until homogeneous to obtain solution A; mix acetic acid, double-distilled water and anhydrous ethanol at a mass ratio of 1:1:4.5 and stir until homogeneous to obtain solution B; under stirring at 200 rpm, add solution B dropwise at a mass ratio of 0.85 times that of solution A, react for 40-60 min, add formamide at a mass ratio of 0.08 times that of tetrabutyl titanate and layered tungsten disulfide at a mass ratio of 0.8-1.2 times that of tetrabutyl titanate, stir until homogeneous, and let stand to form a gel;
[0010] (2) The gel was aged at 40℃ for 24 hours, then soaked twice, filtered, and anhydrous ethanol with a mass of 2 times that of tetrabutyl titanate was added. After standing for 24 hours, it was filtered, dried at room temperature for 24 hours, and then dried at 60℃ for 12 hours to obtain titanium / tungsten particles. The titanium / tungsten particles and urea were mixed at a mass ratio of 1:1 to 1:4, calcined at 500 to 620℃ for 2 hours, and then heated to 800 to 820℃ and calcined for 4 hours to obtain oxygen-rich defect titanium / tungsten particles. Sodium chloropalladium, methanol and water were added. The solution was mixed at a mass ratio of 1:1700 to 1:1800, and the mass ratio of methanol to deionized water in the methanol-water solution was 0.791:1. The mixture was stirred at 80 rpm for 10 to 15 min to obtain a reaction solution. Oxygen-rich defective titanium / tungsten particles were immersed in the reaction solution at a material-to-liquid ratio of 1:10 to 1:30. The mixture was irradiated with a 500W xenon lamp for 60 to 180 s, filtered, and dried at 100℃ for 24 h to obtain a composite photocatalyst. The composite photocatalyst was obtained by carboxylation treatment.
[0011] (3) Mix isoxazole compound, dichloromethane, potassium carbonate, and iodomethane in a mass ratio of 1:15:1.5:0.6 to 1:23:1.5:0.7, stir at 60 to 80 rpm for 10 to 12 hours, extract, wash three times with sodium nitrite standard solution and deionized water, take the organic phase, and dry at 45°C for 10 hours to obtain intermediate D; mix intermediate D, hydrazine hydrate, and ethanol in a mass ratio of 1:6:70 to 1:7:75, stir at 80°C and 80 rpm for 4 to 6 hours, remove by rotary evaporation at -0.07 MPa and 45°C for 3 to 4 hours, extract, wash the organic phase three times with saturated sodium chloride solution, distill at -0.08 MPa and 58°C under reduced pressure for 2 hours, and dry at 70°C for 12 hours to obtain antibacterial agent;
[0012] (4) Epoxy resin E-51, polyethylene glycol 200, and 1,4-dioxane are mixed in a mass ratio of 15:58:8 to 18:66:12. After stirring evenly, 0.1 to 0.3 times the mass of epoxy resin E-51 is added to the carboxylated composite photocatalyst. After ultrasonic dispersion at 700 to 900 W for 30 min, 0.01 to 0.08 times the mass of epoxy resin E-51 is added to the antibacterial agent and 0.0003 times the mass of epoxy resin E-51 is added to the dimethylaminopyridine. After stirring evenly, the mixture is poured into a sealed mold and reacted in an 80°C water bath for 8 h. After drying in a 60°C oven for 2 to 4 h, the mixture is freeze-dried at -30°C for 2 to 4 h. The above alternating hot and cold drying is repeated 1 to 3 times to obtain nanoparticles.
[0013] (5) Polyethylene, nanoparticles, and maleic anhydride-grafted polyethylene are mixed in a mass ratio of 90:10:5 to 90:10:10 and extruded and granulated at 180 to 200°C. The first extruded material is obtained by irradiation. The first extruded material, curing agent D230, calcium carbonate, tributyl citrate, and γ-chloropropyltriethoxysilane are mixed in a mass ratio of 1:0.01:0.05:0.05:0.05 to 1:0.01:0.1:0.1:0.1 and extruded at 200 to 230°C. After cooling for 5 to 10 minutes, the mixture is blown into a film, shaped and cooled, and then cut to obtain antibacterial plastic inner bag material.
[0014] Further, the preparation method of the layered tungsten disulfide in step (1) is as follows: dissolve sodium tungstate dihydrate in ultrapure water at a mass of 80.5 times that of sodium tungstate dihydrate, add hydrochloric acid to make the solution pH 6.5, add L-cysteine solution at a mass of 162 times that of sodium tungstate dihydrate, the mass ratio of L-cysteine to deionized water in the L-cysteine solution is 1:100, sonicate at 400-600W for 10 min, transfer to a polytetrafluoroethylene-lined stainless steel autoclave and seal, heat at 240℃ for 24 h, cool to room temperature, wash three times by centrifugation at 8000 rpm with ultrapure water and ethanol respectively, take the precipitate, and dry at 80℃ for 24 h to obtain layered tungsten disulfide.
[0015] Further, the soaking process in step (2) is as follows: add anhydrous ethanol at 3.2 times the mass of tetrabutyl titanate, let stand at 60°C for 24 hours, filter, add silicate solution at 3.5 times the mass of tetrabutyl titanate, the mass ratio of tetraethyl orthosilicate to ethanol in the silicate solution is 1:0.84, and let stand at 60°C for 24 hours.
[0016] Further, the specific steps of the carboxylation treatment in step (2) are as follows: the composite photocatalyst and anhydrous ethanol are mixed at a mass ratio of 1:16, stirred at 200 rpm for 30-40 min, and then 6.5-10.6 times the mass of the composite photocatalyst in a malonic acid aqueous solution is added. The mass ratio of malonic acid to deionized water in the malonic acid aqueous solution is 1:0.9-1:2.0. After ultrasonic dispersion at 1600W for 30-40 min, the mixture is stirred at 500 rpm and 60℃ for 4-5 h, then centrifuged at 10000 rpm for 20 min, washed 5 times with anhydrous ethanol, the precipitate is collected, and freeze-dried at -30℃ for 24 h to obtain the carboxylated composite photocatalyst.
[0017] Furthermore, the method for preparing the isoxazole compound in step (3) is as follows:
[0018] A. 4-Bromo-3-mercaptobenzoic acid, vinyl butyl ether, 1,3-bis(diphenylphosphine)propane, palladium acetate, and butanol were mixed in a mass ratio of 1:2.0:0.08:0.03:20 to 1:2.5:0.09:0.03:24. The mixture was reacted at 100–115 °C for 5–8 h. After cooling to room temperature, hydrochloric acid was added until the pH of the solution was 2. The mixture was extracted, dried with calcium sulfate for 1 h, filtered, and then distilled under reduced pressure at -0.07 MPa and 60 °C for 3–4 h to obtain intermediate A.
[0019] B. Mix intermediate A, potassium carbonate, sodium laurylate, 4-(hydroxymethyl)-3-vinylacetophenone, and deionized water in a mass ratio of 1:0.9:0.06:1.0:30 to 1:0.9:0.06:1.5:36. React at 60°C for 4 to 8 hours. Add hydrochloric acid until the pH of the solution is 2. Extract the solution, dry it with calcium sulfate for 1 hour, filter it, and dry it at 80°C for 18 hours to obtain intermediate B.
[0020] C. Mix intermediate B, triethylamine, and dichloromethane in a mass ratio of 1:0.1:15 to 1:0.3:22. React at room temperature for 4 to 6 hours, then heat to 45°C and continue reacting for 3 to 5 hours. Add 0.02 to 0.03 times the mass of intermediate B of 4-dimethylaminopyridine and 6 to 10 times the mass of intermediate B of toluene. Heat to 60°C and stir at 80 rpm for 1 to 2 hours. Add 0.4 to 0.5 times the mass of intermediate B of acetic anhydride. React at 60°C for 3 to 5 hours. Add hydrochloric acid until the pH of the solution is 2. Extract, dry with calcium sulfate for 1 hour, filter, and distill under reduced pressure at -0.08 MPa and 68°C for 3 hours to obtain intermediate C.
[0021] D. Mix intermediate C, toluene, and p-tert-butylcatechol in a mass ratio of 1:6:0.0002 to 1:10:0.0002. React at 90–105 °C for 30 min. Add 0.4–0.5 times the mass of intermediate C to m-methoxystyrene and continue the reaction for 8–10 h. Cool to room temperature and wash twice with a 2% sodium bicarbonate aqueous solution. Add 3–4 times the mass of intermediate C to a 10% hydrochloric acid aqueous solution. Separate the layers. Add sodium hydroxide aqueous solution to the organic phase until the pH of the solution is 10–11. Extract the solution. Distill under reduced pressure at -0.08 MPa and 68 °C for 3 h. Dry at 50 °C for 24 h to obtain the isoxazole compound.
[0022] Furthermore, the specific irradiation conditions in step (5) are as follows: 200,000 Curies at a dose rate of 120 Gy / min at room temperature. 60 Irradiation was performed using a Co-γ ray source for 3–5 hours, with an irradiation dose of 12–22 kGy.
[0023] Compared with the prior art, the beneficial effects achieved by the present invention are:
[0024] This invention modifies a composite photocatalyst by carboxylation and embeds it into a modified resin to form nanoparticles. While the side chains of the modified resin anchor the composite photocatalyst, electrostatic repulsion occurs between the composite photocatalysts, resulting in voids inside the nanoparticles. After repeated hot and cold drying, the resin in the voids cracks and collapses, forming a porous structure that reflects and refracts sunlight, allowing sunlight to enter the interior and promoting the photocatalytic performance of the composite photocatalyst, thus initiating the degradation of the plastic inner bag material.
[0025] First, this invention uses a composite of layered tungsten disulfide and titanium dioxide sol to form a porous titanium dioxide aerogel that encapsulates the tungsten disulfide. Due to the layered structure of the tungsten disulfide and the porous structure of the aerogel, the composite photocatalyst has a large specific surface area, improving its light absorption capacity. Furthermore, the reaction with urea during calcination creates an oxygen-rich defect surface, promoting interfacial bonding between the aerogel and tungsten disulfide, facilitating electron transfer, and aiding in the separation of photogenerated electron-hole pairs. This enhances the photocatalytic performance of titanium dioxide and improves the photodegradability of the plastic inner bag material. Simultaneously, the presence of tungsten disulfide facilitates the conversion of absorbed light energy into heat energy, increasing the temperature during photodegradation and further accelerating the photodegradation rate of the plastic inner bag material. Next, palladium is deposited in the pores and surface of the aerogel. Oxygen vacancies on the aerogel surface induce palladium to interact with the aerogel, further enhancing photocatalytic activity and improving the photodegradability of the plastic inner bag material.
[0026] Secondly, after the bromine of 4-bromo-3-mercaptobenzoic acid is replaced by the ketone group, the ketone group condenses with the ketone group of 4-(hydroxymethyl)-3-vinylacetophenone to form a cyclization and form isoxazole, which effectively inhibits bacterial growth and gives the plastic inner bag material antibacterial properties. After the carboxyl group of 4-bromo-3-mercaptobenzoic acid is esterified, the resulting methyl ester reacts with hydrazine hydrate to form an acyl hydrazine structure, which assists the isoxazole group and jointly improves the antibacterial properties of the plastic inner bag material. Next, on the surface of the carboxylated composite photocatalyst, epoxy resin and the thiol group of the antibacterial agent crosslink and polymerize to form a modified resin layer. The hydroxyl groups in the side chains of the modified resin molecules can bond with some of the carboxyl groups of the composite photocatalyst, so that the two combine to form nanoparticles. Then, the double bonds in the nanoparticles are grafted onto irradiated polyethylene, and maleic anhydride grafted onto polyethylene is used as a compatibilizing phase to promote the compatibility of the nanoparticles with the polyethylene base material and improve the performance of the plastic inner bag material. Detailed Implementation
[0027] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0028] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The test methods for various indicators of the antibacterial plastic inner bag material prepared in the following embodiments are as follows:
[0029] Antibacterial: Take examples and comparative examples of the same size and test the antibacterial rate according to QB / T2591.
[0030] Photodegradation: The degradation rate was tested using examples and comparative examples of the same size according to GB / T20197.
[0031] Example 1
[0032] (1) Dissolve sodium tungstate dihydrate in 80.5 times the mass of sodium tungstate dihydrate in ultrapure water, add hydrochloric acid to the pH of the solution to 6.5, add L-cysteine solution with 162 times the mass of sodium tungstate dihydrate, the mass ratio of L-cysteine to deionized water in the L-cysteine solution is 1:100, sonicate at 400W for 10 min, transfer to a polytetrafluoroethylene-lined stainless steel autoclave and seal, heat at 240℃ for 24 h, cool to room temperature, wash three times by centrifugation at 8000 rpm with ultrapure water and ethanol respectively, take the precipitate, dry at 80℃ for 24 h to obtain layered tungsten disulfide;
[0033] (2) Mix tetrabutyl titanate and anhydrous ethanol at a mass ratio of 1:1.44 and stir until homogeneous to obtain solution A; mix acetic acid, double-distilled water and anhydrous ethanol at a mass ratio of 1:1:4.5 and stir until homogeneous to obtain solution B; under stirring at 200 rpm, add solution B dropwise at a mass ratio of 0.85 times that of solution A, react for 40 min, add formamide at a mass ratio of 0.08 times that of tetrabutyl titanate and layered tungsten disulfide at a mass ratio of 0.8 times that of tetrabutyl titanate, stir until homogeneous, and let stand to form a gel;
[0034] (3) The gel was aged at 40℃ for 24 hours, then anhydrous ethanol (3.2 times the mass of tetrabutyl titanate) was added. After standing at 60℃ for 24 hours, the gel was filtered. Then, a silicate solution (3.5 times the mass of tetrabutyl titanate) was added, with a mass ratio of tetraethyl orthosilicate to ethanol of 1:0.84. The gel was stood at 60℃ for 24 hours. The above process of soaking in anhydrous ethanol and silicate solution was repeated once. After filtration, anhydrous ethanol (2 times the mass of tetrabutyl titanate) was added. After standing for 24 hours, the gel was filtered and dried at room temperature for 24 hours, then dried at 60℃ for 12 hours to obtain titanium / tungsten particles. The titanium / tungsten particles and urea were mixed at a mass ratio of 1:1. The mixture was calcined at 500℃ for 2 hours, then heated to 800℃ and calcined for 4 hours to obtain oxygen-rich defect titanium / tungsten particles. Sodium chloropalladium and methanol aqueous solution were mixed at a mass ratio of 1:1700, with a methanol content of 1:1700. The reaction solution was prepared by stirring at 80 rpm for 10 min with deionized water at a mass ratio of 0.791:1. Oxygen-rich defective titanium / tungsten particles were immersed in the reaction solution at a material-to-liquid ratio of 1:10. The mixture was then irradiated with a 500W xenon lamp for 60 s, filtered, and dried at 100℃ for 24 h to obtain a composite photocatalyst. The composite photocatalyst and anhydrous ethanol were mixed at a mass ratio of 1:16 and stirred at 200 rpm for 30 min. Then, 6.5 times the mass of the composite photocatalyst was added to a malonic acid aqueous solution with a mass ratio of malonic acid to deionized water of 1:0.9. The mixture was ultrasonically dispersed at 1600W for 30 min, stirred at 500 rpm and 60℃ for 4 h, centrifuged at 10000 rpm for 20 min, washed 5 times with anhydrous ethanol, and the precipitate was freeze-dried at -30℃ for 24 h to obtain a carboxylated composite photocatalyst.
[0035] (3) 4-bromo-3-mercaptobenzoic acid, vinyl butyl ether, 1,3-bis(diphenylphosphine)propane, palladium acetate, and butanol were mixed in a mass ratio of 1:2:0.08:0.03:20. After reacting at 100°C for 5 h, the mixture was cooled to room temperature, hydrochloric acid was added until the pH of the solution was 2, and the mixture was extracted. After drying with calcium sulfate for 1 h, the mixture was filtered and distilled under reduced pressure at -0.07 MPa and 60°C for 3 h to obtain intermediate A.
[0036] (4) Mix intermediate A, potassium carbonate, sodium laurylate, 4-(hydroxymethyl)-3-vinylacetophenone, and deionized water in a mass ratio of 1:0.9:0.06:1:30. After reacting at 60°C for 4 hours, add hydrochloric acid until the solution pH is 2, extract, dry with calcium sulfate for 1 hour, filter, and dry at 80°C for 18 hours to obtain intermediate B.
[0037] (5) Mix intermediate B, triethylamine, and dichloromethane in a mass ratio of 1:0.1:15. After reacting at room temperature for 4 hours, heat to 45°C and continue reacting for 3 hours. Then add 0.02 times the mass of intermediate B of 4-dimethylaminopyridine and 6 times the mass of intermediate B of toluene. Heat to 60°C and stir at 80 rpm for 1 hour. Then add 0.4 times the mass of intermediate B of acetic anhydride. After reacting at 60°C for 3 hours, add hydrochloric acid until the solution pH is 2. Extract, dry with calcium sulfate for 1 hour, filter, and distill under reduced pressure at -0.08 MPa and 68°C for 3 hours to obtain intermediate C.
[0038] (6) Mix intermediate C, toluene, and p-tert-butylcatechol in a mass ratio of 1:6:0.0002, react at 90°C for 30 min, add m-methoxystyrene at 0.4 times the mass of intermediate C, continue the reaction for 8 h, cool to room temperature, wash twice with 2% sodium bicarbonate aqueous solution, add 3 times the mass of intermediate C with 10% hydrochloric acid aqueous solution, separate the layers, add sodium hydroxide aqueous solution to the organic phase until the solution pH is 10, extract, distill under reduced pressure at -0.08 MPa and 68°C for 3 h, and dry at 50°C for 24 h to obtain isoxazole compound;
[0039] (7) Mix isoxazole compound, dichloromethane, potassium carbonate and iodomethane in a mass ratio of 1:15:1.5:0.6, stir at 60 rpm for 10 h, extract, wash three times with sodium nitrite standard solution and deionized water respectively, take the organic phase, dry at 45 ℃ for 10 h to obtain intermediate D; mix intermediate D, hydrazine hydrate and ethanol in a mass ratio of 1:6:70, stir at 80 ℃ and 80 rpm for 4 h, remove by rotary evaporation at -0.07 MPa and 45 ℃ for 3 h, extract, wash the organic phase three times with saturated sodium chloride solution, distill at -0.08 MPa and 58 ℃ under reduced pressure for 2 h, and dry at 70 ℃ for 12 h to obtain antibacterial agent;
[0040] (8) Epoxy resin E-51, polyethylene glycol 200 and 1,4-dioxane were mixed in a mass ratio of 15:58:8 and stirred evenly. Then, 0.1 times the mass of epoxy resin E-51 carboxylated composite photocatalyst was added. After ultrasonic dispersion at 700W for 30 min, 0.01 times the mass of epoxy resin E-51 antibacterial agent and 0.0003 times the mass of epoxy resin E-51 dimethylaminopyridine were added. After stirring evenly, the mixture was poured into a sealed mold and reacted in an 80℃ water bath for 8 h. After drying in a 60℃ oven for 2 h, the mixture was freeze-dried at -30℃ for 2 h. The above alternating hot and cold drying was repeated once to obtain nanoparticles.
[0041] (9) Polyethylene, nanoparticles, and maleic anhydride-grafted polyethylene are mixed at a mass ratio of 90:10:5, extruded and granulated at 180-200°C, and then granulated at room temperature with 200,000 Curies at a dosage rate of 120 Gy / min. 60 Irradiation with a Co-γ ray source for 3 hours and an irradiation dose of 12 kGy yields the first extrusion material. The first extrusion material, curing agent D230, calcium carbonate, tributyl citrate, and γ-chloropropyltriethoxysilane are mixed in a mass ratio of 1:0.01:0.05:0.05:0.05 and extruded at 200–230°C. After cooling for 5 minutes, the mixture is blown into a film, shaped, cooled, and slit to obtain the antibacterial plastic inner bag material.
[0042] Example 2
[0043] (1) Dissolve sodium tungstate dihydrate in 80.5 times the mass of sodium tungstate dihydrate in ultrapure water, add hydrochloric acid to make the solution pH 6.5, add L-cysteine solution with 162 times the mass of sodium tungstate dihydrate, the mass ratio of L-cysteine to deionized water in the L-cysteine solution is 1:100, sonicate at 500W for 10 min, transfer to a polytetrafluoroethylene-lined stainless steel autoclave and seal, heat at 240℃ for 24 h, cool to room temperature, wash three times by centrifugation at 8000 rpm with ultrapure water and ethanol respectively, take the precipitate, dry at 80℃ for 24 h to obtain layered tungsten disulfide;
[0044] (2) Mix tetrabutyl titanate and anhydrous ethanol at a mass ratio of 1:1.44 and stir until homogeneous to obtain solution A; mix acetic acid, double-distilled water and anhydrous ethanol at a mass ratio of 1:1:4.5 and stir until homogeneous to obtain solution B; under stirring at 200 rpm, add solution B dropwise at a mass ratio of 0.85 times that of solution A, react for 50 min, add formamide at a mass ratio of 0.08 times that of tetrabutyl titanate and layered tungsten disulfide at a mass ratio of 1 times that of tetrabutyl titanate, stir until homogeneous, and let stand to form a gel;
[0045] (3) The gel was aged at 40℃ for 24 hours, then anhydrous ethanol (3.2 times the mass of tetrabutyl titanate) was added. After aging at 60℃ for 24 hours, the gel was filtered. Then, a silicate solution (3.5 times the mass of tetrabutyl titanate) was added, with a mass ratio of tetraethyl orthosilicate to ethanol of 1:0.84. The gel was aged at 60℃ for 24 hours. The above process of soaking in anhydrous ethanol and silicate solution was repeated once. After filtration, anhydrous ethanol (2 times the mass of tetrabutyl titanate) was added. The gel was aged at 60℃ for 24 hours, then dried at room temperature for 24 hours, and then dried at 60℃ for 12 hours to obtain titanium / tungsten particles. The titanium / tungsten particles and urea were mixed at a mass ratio of 1:2.5, calcined at 560℃ for 2 hours, and then calcined at 810℃ for 4 hours to obtain oxygen-rich defect titanium / tungsten particles. Sodium chloropalladium and methanol aqueous solution were mixed at a mass ratio of 1:1750, with a mass ratio of methanol to ethanol of 1:1750. The reaction solution was prepared by stirring at 80 rpm for 12 min with deionized water at a mass ratio of 0.791:1. Oxygen-rich defective titanium / tungsten particles were immersed in the reaction solution at a material-to-liquid ratio of 1:20. The mixture was then irradiated with a 500W xenon lamp for 120 s, filtered, and dried at 100℃ for 24 h to obtain a composite photocatalyst. The composite photocatalyst and anhydrous ethanol were mixed at a mass ratio of 1:16 and stirred at 200 rpm for 35 min. Then, 8.6 times the mass of the composite photocatalyst was added to a malonic acid aqueous solution with a mass ratio of malonic acid to deionized water of 1:1.4. The mixture was ultrasonically dispersed at 1600W for 35 min, stirred at 500 rpm and 60℃ for 4.5 h, centrifuged at 10000 rpm for 20 min, washed 5 times with anhydrous ethanol, and the precipitate was freeze-dried at -30℃ for 24 h to obtain a carboxylated composite photocatalyst.
[0046] (3) 4-bromo-3-mercaptobenzoic acid, vinyl butyl ether, 1,3-bis(diphenylphosphine)propane, palladium acetate, and butanol were mixed in a mass ratio of 1:2.25:0.085:0.03:22 and reacted at 107°C for 6.5 h. After cooling to room temperature, hydrochloric acid was added until the pH of the solution was 2. The mixture was extracted, dried with calcium sulfate for 1 h, filtered, and then distilled under reduced pressure at -0.07 MPa and 60°C for 3.5 h to obtain intermediate A.
[0047] (4) Mix intermediate A, potassium carbonate, sodium laurylate, 4-(hydroxymethyl)-3-vinylacetophenone, and deionized water in a mass ratio of 1:0.9:0.06:1.25:33. After reacting at 60°C for 6 hours, add hydrochloric acid until the solution pH is 2, extract, dry with calcium sulfate for 1 hour, filter, and dry at 80°C for 18 hours to obtain intermediate B.
[0048] (5) Mix intermediate B, triethylamine, and dichloromethane in a mass ratio of 1:0.2:18.5. After reacting at room temperature for 5 hours, raise the temperature to 45°C and continue reacting for 4 hours. Then add 0.025 times the mass of intermediate B of 4-dimethylaminopyridine and 8 times the mass of intermediate B of toluene. Raise the temperature to 60°C and stir at 80 rpm for 1.5 hours. Then add 0.45 times the mass of intermediate B of acetic anhydride. After reacting at 60°C for 4 hours, add hydrochloric acid until the solution pH is 2. Extract, dry with calcium sulfate for 1 hour, filter, and distill under reduced pressure at -0.08 MPa and 68°C for 3 hours to obtain intermediate C.
[0049] (6) Intermediate C, toluene, and p-tert-butylcatechol were mixed in a mass ratio of 1:8:0.0002 and reacted at 97°C for 30 min. Then, 0.45 times the mass of intermediate C was added to m-methoxystyrene and the reaction was continued for 9 h. The mixture was cooled to room temperature and washed twice with a 2% sodium bicarbonate aqueous solution. Then, 3.5 times the mass of intermediate C was added to a 10% hydrochloric acid aqueous solution. The mixture was separated into layers. Sodium hydroxide aqueous solution was added to the organic phase until the pH of the solution was 10.5. The mixture was extracted and distilled under reduced pressure at -0.08 MPa and 68°C for 3 h. The mixture was then dried at 50°C for 24 h to obtain the isoxazole compound.
[0050] (7) Mix isoxazole compound, dichloromethane, potassium carbonate and iodomethane in a mass ratio of 1:19:1.5:0.65, stir at 70 rpm for 11 h, extract, wash three times with sodium nitrite standard solution and deionized water respectively, take the organic phase, dry at 45 ℃ for 10 h to obtain intermediate D; mix intermediate D, hydrazine hydrate and ethanol in a mass ratio of 1:6.5:72.5, stir at 80 ℃ and 80 rpm for 5 h, remove by rotary evaporation at -0.07 MPa and 45 ℃ for 3.5 h, extract, wash the organic phase three times with saturated sodium chloride solution, distill at -0.08 MPa and 58 ℃ under reduced pressure for 2 h, and dry at 70 ℃ for 12 h to obtain antibacterial agent;
[0051] (8) Epoxy resin E-51, polyethylene glycol 200 and 1,4-dioxane were mixed in a mass ratio of 16.5:62:10. After stirring evenly, 0.2 times the mass of epoxy resin E-51 carboxylated composite photocatalyst was added. After ultrasonic dispersion at 800W for 30min, 0.045 times the mass of epoxy resin E-51 antibacterial agent and 0.0003 times the mass of epoxy resin E-51 dimethylaminopyridine were added. After stirring evenly, the mixture was poured into a sealed mold and reacted in an 80℃ water bath for 8h. After drying in a 60℃ oven for 3h, the mixture was freeze-dried at -30℃ for 3h. The above alternating hot and cold drying was repeated twice to obtain nanoparticles.
[0052] (9) Polyethylene, nanoparticles, and maleic anhydride-grafted polyethylene are mixed at a mass ratio of 90:10:7.5, extruded and granulated at 180–200°C, and then granulated at room temperature using 200,000 Curies at a dosage rate of 120 Gy / min. 60 Irradiation with a Co-γ ray source for 4 hours at a dose of 17 kGy yields the first extrusion material. The first extrusion material, curing agent D230, calcium carbonate, tributyl citrate, and γ-chloropropyltriethoxysilane are mixed in a mass ratio of 1:0.01:0.075:0.075:0.075 and extruded at 200–230°C. After cooling for 7 minutes, the mixture is blown into a film, shaped, cooled, and slit to obtain the antibacterial plastic inner bag material.
[0053] Example 3
[0054] (1) Dissolve sodium tungstate dihydrate in 80.5 times the mass of sodium tungstate dihydrate in ultrapure water, add hydrochloric acid to the pH of the solution to 6.5, add L-cysteine solution with 162 times the mass of sodium tungstate dihydrate, the mass ratio of L-cysteine to deionized water in the L-cysteine solution is 1:100, sonicate at 600W for 10 min, transfer to a polytetrafluoroethylene-lined stainless steel autoclave and seal, heat at 240℃ for 24 h, cool to room temperature, wash three times by centrifugation at 8000 rpm with ultrapure water and ethanol respectively, take the precipitate, dry at 80℃ for 24 h to obtain layered tungsten disulfide;
[0055] (2) Mix tetrabutyl titanate and anhydrous ethanol at a mass ratio of 1:1.44 and stir until homogeneous to obtain solution A; mix acetic acid, double-distilled water and anhydrous ethanol at a mass ratio of 1:1:4.5 and stir until homogeneous to obtain solution B; under stirring at 200 rpm, add solution B dropwise at a mass ratio of 0.85 times that of solution A, react for 60 min, add formamide at a mass ratio of 0.08 times that of tetrabutyl titanate and layered tungsten disulfide at a mass ratio of 1.2 times that of tetrabutyl titanate, stir until homogeneous, and let stand to form a gel;
[0056] (3) The gel was aged at 40℃ for 24 hours, then anhydrous ethanol (3.2 times the mass of tetrabutyl titanate) was added. After standing at 60℃ for 24 hours, the gel was filtered. Then, a silicate solution (3.5 times the mass of tetrabutyl titanate) was added, with a mass ratio of tetraethyl orthosilicate to ethanol of 1:0.84. The gel was stood at 60℃ for 24 hours. The above process of soaking in anhydrous ethanol and silicate solution was repeated once. After filtration, anhydrous ethanol (2 times the mass of tetrabutyl titanate) was added. After standing for 24 hours, the gel was filtered and dried at room temperature for 24 hours, then dried at 60℃ for 12 hours to obtain titanium / tungsten particles. The titanium / tungsten particles and urea were mixed at a mass ratio of 1:4. The mixture was calcined at 620℃ for 2 hours, then heated to 820℃ and calcined for 4 hours to obtain oxygen-rich defect titanium / tungsten particles. Sodium chloropalladium and methanol aqueous solution were mixed at a mass ratio of 1:1800, with a mass ratio of methanol in the methanol aqueous solution. The reaction solution was prepared by stirring at 80 rpm for 15 min with deionized water at a mass ratio of 0.791:1. Oxygen-rich defective titanium / tungsten particles were immersed in the reaction solution at a material-to-liquid ratio of 1:30. The mixture was then irradiated with a 500W xenon lamp for 180 s, filtered, and dried at 100℃ for 24 h to obtain a composite photocatalyst. The composite photocatalyst and anhydrous ethanol were mixed at a mass ratio of 1:16 and stirred at 200 rpm for 40 min. Then, 10.6 times the mass of the composite photocatalyst was added to a malonic acid aqueous solution with a mass ratio of malonic acid to deionized water of 1:2. The mixture was ultrasonically dispersed at 1600W for 40 min, stirred at 500 rpm and 60℃ for 5 h, centrifuged at 10000 rpm for 20 min, washed 5 times with anhydrous ethanol, and the precipitate was freeze-dried at -30℃ for 24 h to obtain a carboxylated composite photocatalyst.
[0057] (3) 4-bromo-3-mercaptobenzoic acid, vinyl butyl ether, 1,3-bis(diphenylphosphine)propane, palladium acetate, and butanol were mixed in a mass ratio of 1:2.5:0.09:0.03:24. After reacting at 115°C for 8 hours, the mixture was cooled to room temperature, hydrochloric acid was added until the pH of the solution was 2, and the mixture was extracted. After drying with calcium sulfate for 1 hour, the mixture was filtered and distilled under reduced pressure at -0.07 MPa and 60°C for 4 hours to obtain intermediate A.
[0058] (4) Mix intermediate A, potassium carbonate, sodium laurylate, 4-(hydroxymethyl)-3-vinylacetophenone, and deionized water in a mass ratio of 1:0.9:0.06:1.5:36, react at 60°C for 8 hours, add hydrochloric acid until the solution pH is 2, extract, dry with calcium sulfate for 1 hour, filter, and dry at 80°C for 18 hours to obtain intermediate B;
[0059] (5) Mix intermediate B, triethylamine, and dichloromethane in a mass ratio of 1:0.3:22. After reacting at room temperature for 6 hours, raise the temperature to 45°C and continue reacting for 5 hours. Then add 0.03 times the mass of intermediate B of 4-dimethylaminopyridine and 10 times the mass of intermediate B of toluene. Raise the temperature to 60°C and stir at 80 rpm for 2 hours. Then add 0.5 times the mass of intermediate B of acetic anhydride. After reacting at 60°C for 5 hours, add hydrochloric acid until the solution pH is 2. Extract, dry with calcium sulfate for 1 hour, filter, and distill under reduced pressure at -0.08 MPa and 68°C for 3 hours to obtain intermediate C.
[0060] (6) Mix intermediate C, toluene, and p-tert-butylcatechol in a mass ratio of 1:10:0.0002, react at 105°C for 30 min, add m-methoxystyrene at 0.5 times the mass of intermediate C, continue the reaction for 10 h, cool to room temperature, wash twice with 2% sodium bicarbonate aqueous solution, add 4 times the mass of intermediate C with 10% hydrochloric acid aqueous solution, separate the layers, add sodium hydroxide aqueous solution to the organic phase until the solution pH is 11, extract, distill under reduced pressure at -0.08 MPa and 68°C for 3 h, and dry at 50°C for 24 h to obtain isoxazole compound;
[0061] (7) Mix isoxazole compound, dichloromethane, potassium carbonate and iodomethane in a mass ratio of 1:23:1.5:0.7, stir at 80 rpm for 12 h, extract, wash three times with sodium nitrite standard solution and deionized water respectively, take the organic phase, dry at 45 ℃ for 10 h to obtain intermediate D; mix intermediate D, hydrazine hydrate and ethanol in a mass ratio of 1:7:75, stir at 80 ℃ and 80 rpm for 6 h, remove by rotary evaporation at -0.07 MPa and 45 ℃ for 4 h, extract, wash the organic phase three times with saturated sodium chloride solution, distill at -0.08 MPa and 58 ℃ under reduced pressure for 2 h, and dry at 70 ℃ for 12 h to obtain antibacterial agent;
[0062] (8) Epoxy resin E-51, polyethylene glycol 200 and 1,4-dioxane were mixed in a mass ratio of 18:66:12. After stirring evenly, 0.3 times the mass of epoxy resin E-51 carboxylated composite photocatalyst was added. After ultrasonic dispersion at 900W for 30min, 0.08 times the mass of epoxy resin E-51 antibacterial agent and 0.0003 times the mass of epoxy resin E-51 dimethylaminopyridine were added. After stirring evenly, the mixture was poured into a sealed mold and reacted in an 80℃ water bath for 8h. After drying in a 60℃ oven for 4h, it was freeze-dried at -30℃ for 4h. The above alternating hot and cold drying was repeated 3 times to obtain nanoparticles.
[0063] (9) Polyethylene, nanoparticles, and maleic anhydride-grafted polyethylene are mixed at a mass ratio of 90:10:10, extruded and granulated at 180-200°C, and then granulated at room temperature with 200,000 Curies at a dosage rate of 120 Gy / min.60 Irradiation with a Co-γ ray source for 5 hours and an irradiation dose of 22 kGy yields the first extrusion material. The first extrusion material, curing agent D230, calcium carbonate, tributyl citrate, and γ-chloropropyltriethoxysilane are mixed in a mass ratio of 1:0.01:0.1:0.1:0.1 and extruded at 200–230°C. After cooling for 10 minutes, the mixture is blown into a film, shaped, cooled, and slit to obtain the antibacterial plastic inner bag material.
[0064] Comparative Example 1
[0065] The difference between Comparative Example 1 and Example 2 is that step (1) is omitted, and step (2) is changed to: mixing tetrabutyl titanate and anhydrous ethanol at a mass ratio of 1:1.44 and stirring until homogeneous to obtain solution A; mixing acetic acid, double-distilled water, and anhydrous ethanol at a mass ratio of 1:1:4.5 and stirring until homogeneous to obtain solution B; adding solution B at a mass of 0.85 times that of solution A dropwise to solution A while stirring at 200 rpm, reacting for 50 min, adding formamide at a mass of 0.08 times that of tetrabutyl titanate, stirring until homogeneous, and allowing to stand to form a gel. The remaining steps are the same as in Example 2.
[0066] Comparative Example 2
[0067] The difference between Comparative Example 2 and Example 2 lies in step (3). Step (3) is changed as follows: the gel is aged at 40°C for 24 hours, anhydrous ethanol with a mass of 3.2 times that of tetrabutyl titanate is added, and the gel is aged at 60°C for 24 hours. After filtration, a silicate solution with a mass of 3.5 times that of tetrabutyl titanate is added. The mass ratio of tetraethyl orthosilicate to ethanol in the silicate solution is 1:0.84. The gel is aged at 60°C for 24 hours. The above process of soaking in anhydrous ethanol and silicate solution is repeated once. After filtration, anhydrous ethanol with a mass of 2 times that of tetrabutyl titanate is added. The gel is aged at 24 hours, filtered, dried at room temperature for 24 hours, and then dried at 60°C for 12 hours to obtain titanium / tungsten particles. Sodium chloropalladium and methanol aqueous solution are mixed at a mass ratio of 1:1750. The mass ratio of methanol to deionized water in the methanol aqueous solution is 0. The reaction solution was prepared by stirring at 80 rpm for 12 min with a ratio of 791:1. Titanium / tungsten particles were immersed in the reaction solution at a ratio of 1:20. The mixture was irradiated with a 500W xenon lamp for 120 s, filtered, and dried at 100℃ for 24 h to obtain a composite photocatalyst. The composite photocatalyst and anhydrous ethanol were mixed at a mass ratio of 1:16 and stirred at 200 rpm for 35 min. Then, 8.6 times the mass of the composite photocatalyst in a malonic acid aqueous solution was added, with a malonic acid to deionized water mass ratio of 1:1.4. The mixture was ultrasonically dispersed at 1600W for 35 min, stirred at 500 rpm and 60℃ for 4.5 h, and then centrifuged at 10000 rpm for 20 min. The mixture was washed 5 times with anhydrous ethanol, and the precipitate was collected and freeze-dried at -30℃ for 24 h to obtain a carboxylated composite photocatalyst. The remaining steps were the same as in Example 2.
[0068] Comparative Example 3
[0069] The difference between Comparative Example 3 and Example 2 lies in step (3). Step (3) is changed to: aging the gel at 40°C for 24 hours, adding anhydrous ethanol at 3.2 times the mass of tetrabutyl titanate, aging at 60°C for 24 hours, filtering, adding silicate solution at 3.5 times the mass of tetrabutyl titanate, with a mass ratio of tetraethyl orthosilicate to ethanol of 1:0.84, aging at 60°C for 24 hours, repeating the above anhydrous ethanol and silicate solution soaking process once, filtering, adding anhydrous ethanol at 2 times the mass of tetrabutyl titanate, aging for 24 hours, filtering, drying at room temperature for 24 hours, and then drying at 60°C for 12 hours to obtain titanium / tungsten particles; the titanium / tungsten particles and urea are mixed according to the mass ratio The mixture was prepared by mixing in a 1:2.5 ratio and calcining at 560℃ for 2 hours, followed by calcination at 810℃ for 4 hours to obtain oxygen-enriched defective titanium / tungsten particles. These particles were then mixed with anhydrous ethanol at a mass ratio of 1:16 and stirred at 200 rpm for 35 minutes. An aqueous solution of malonic acid, with a mass ratio of malonic acid to deionized water of 1:1.4, was added. The mixture was ultrasonically dispersed at 1600 W for 35 minutes, then stirred at 500 rpm and 60℃ for 4.5 hours. The mixture was then centrifuged at 10000 rpm for 20 minutes, washed five times with anhydrous ethanol, and the precipitate was freeze-dried at -30℃ for 24 hours to obtain a carboxylated composite photocatalyst. The remaining steps were the same as in Example 2.
[0070] Comparative Example 4
[0071] The difference between Comparative Example 4 and Example 2 lies in step (3). Step (3) is changed to: aging the gel at 40°C for 24 hours, adding anhydrous ethanol at 3.2 times the mass of tetrabutyl titanate, aging at 60°C for 24 hours, filtering, adding silicate solution at 3.5 times the mass of tetrabutyl titanate (the mass ratio of tetraethyl orthosilicate to ethanol in the silicate solution is 1:0.84), aging at 60°C for 24 hours, repeating the above anhydrous ethanol and silicate solution soaking process once, filtering, adding anhydrous ethanol at 2 times the mass of tetrabutyl titanate, aging for 24 hours, filtering, drying at room temperature for 24 hours, and then... Titanium / tungsten particles were obtained by drying at 60℃ for 12 hours. These particles and urea were mixed at a mass ratio of 1:2.5, calcined at 560℃ for 2 hours, and then calcined at 810℃ for 4 hours to obtain oxygen-rich defective titanium / tungsten particles. Sodium chloropalladium and a methanol-water solution were mixed at a mass ratio of 1:1750 (the mass ratio of methanol to deionized water in the methanol-water solution was 0.791:1), and stirred at 80 rpm for 12 minutes to obtain a reaction solution. The oxygen-rich defective titanium / tungsten particles were immersed in the reaction solution at a material-to-liquid ratio of 1:20, irradiated with a 500W xenon lamp for 120 seconds, filtered, and dried at 100℃ for 24 hours to obtain a composite photocatalyst. The remaining steps were the same as in Example 2.
[0072] Comparative Example 5
[0073] The difference between Comparative Example 5 and Example 2 is that steps (3) to (6) are omitted, and step (7) is changed to: 4-bromo-3-mercaptobenzoic acid, dichloromethane, potassium carbonate, and iodomethane are mixed in a mass ratio of 1:19:1.5:0.65, stirred at 70 rpm for 11 h, extracted, washed three times with sodium nitrite standard solution and deionized water, and the organic phase is dried at 45 °C for 10 h to obtain intermediate D; intermediate D, hydrazine hydrate, and ethanol are mixed in a mass ratio of 1:6.5:72.5, stirred at 80 °C and 80 rpm for 5 h, evaporated under vacuum of -0.07 MPa at 45 °C for 3.5 h, extracted, washed three times with saturated sodium chloride solution, distilled under reduced pressure of -0.08 MPa at 58 °C for 2 h, and dried at 70 °C for 12 h to obtain the antibacterial agent. The remaining steps are the same as in Example 2.
[0074] Comparative Example 6
[0075] The difference between Comparative Example 6 and Example 2 is that step (7) is omitted, and step (8) is changed to: mixing epoxy resin E-51, polyethylene glycol 200, and 1,4-dioxane in a mass ratio of 16.5:62:10, stirring evenly, adding 0.2 times the mass of epoxy resin E-51 carboxylated composite photocatalyst, ultrasonically dispersing at 800W for 30 minutes, adding 0.045 times the mass of epoxy resin E-51 isoxazole compound and 0.0003 times the mass of epoxy resin E-51 dimethylaminopyridine, stirring evenly, and then pouring into a dense The mold was closed, and the mixture was reacted in an 80°C water bath for 8 hours, dried in a 60°C oven for 3 hours, and then freeze-dried at -30°C for 3 hours. This alternating hot and cold drying process was repeated twice to obtain nanoparticles. Step (9) was changed to: mixing polyethylene, nanoparticles, maleic anhydride-grafted polyethylene, curing agent D230, calcium carbonate, tributyl citrate, and γ-chloropropyltriethoxysilane in a mass ratio of 90:10:7.5:1:5:1:1, extruding at 200-230°C, cooling for 7 minutes, blowing film, shaping and cooling, and slitting to obtain antibacterial plastic inner bag material. The remaining steps were the same as in Example 2.
[0076] Comparative Example 7
[0077] The difference between Comparative Example 7 and Example 2 lies in step (8). Step (8) is changed as follows: epoxy resin E-51, polyethylene glycol 200, and 1,4-dioxane are mixed in a mass ratio of 16.5:62:10. After stirring evenly, 0.2 times the mass of epoxy resin E-51 carboxylated composite photocatalyst is added. After ultrasonic dispersion at 800W for 30 minutes, 0.045 times the mass of epoxy resin E-51 antibacterial agent and 0.0003 times the mass of epoxy resin E-51 dimethylaminopyridine are added. After stirring evenly, the mixture is poured into a sealed mold and reacted in an 80°C water bath for 8 hours. Then, it is dried in a 60°C oven for 24 hours to obtain nanoparticles. The remaining steps are the same as in Example 2.
[0078] Example of effect
[0079] Table 1 below shows the performance analysis results of the antibacterial plastic inner bag materials of Examples 1 to 3 and Comparative Examples 1 to 7 of the present invention.
[0080] Table 1
[0081]
[0082] A comparison of the degradation rate experimental data of the examples and comparative examples reveals that the present invention utilizes titanium dioxide aerogel to encapsulate layered tungsten disulfide, facilitating the conversion of absorbed light energy into heat energy and improving the photodegradability of the plastic inner bag material. Further calcination with urea and deposition of palladium metal facilitate the separation of photogenerated electron-hole pairs, enhancing the photocatalytic performance of titanium dioxide and thus improving the photodegradability of the plastic inner bag material. Then, embedding it into modified resin and repeatedly drying it with hot and cold to form a porous structure enhances the reflection and refraction of sunlight, further increasing the photodegradability of the plastic inner bag material. A comparison of the antibacterial rate experimental data of the examples and comparative examples reveals that the present invention utilizes the reaction of 4-bromo-3-mercaptobenzoic acid, 4-(hydroxymethyl)-3-vinylacetophenone, and hydrazine hydrate to form an antibacterial agent. The isoxazole and hydrazide structures in the molecular chain collectively improve the antibacterial properties of the plastic inner bag material. After preparing nanoparticles with a carboxylated composite photocatalyst, cross-linking them with polyethylene through irradiation further enhances the antibacterial properties of the plastic inner bag material.
[0083] It will be apparent to those skilled in the art that the present 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 its spirit or essential characteristics. 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. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.
Claims
1. A type of antibacterial plastic inner bag material, characterized in that, The antibacterial plastic inner bag material is made by co-extruding nanoparticles, polyethylene, and maleic anhydride-grafted polyethylene, followed by irradiation, and then secondary extrusion and blown film preparation with additives.
2. The antibacterial plastic inner bag material according to claim 1, characterized in that, The nanoparticles are prepared by mixing epoxy resin E-51, antibacterial agent, and solvent, adding carboxylated composite photocatalyst, ultrasonically dispersing evenly, reacting in a water bath for a period of time, and then drying by alternating hot and cold temperatures.
3. The antibacterial plastic inner bag material according to claim 2, characterized in that, The composite photocatalyst is prepared by combining layered tungsten disulfide and titanium dioxide precursor sol, drying to form titanium / tungsten particles encapsulated in aerogel, and then calcining with urea to deposit metallic palladium.
4. The antibacterial plastic inner bag material according to claim 2, characterized in that, The antibacterial agent is prepared from 4-bromo-3-mercaptobenzoic acid, 4-(hydroxymethyl)-3-vinylacetophenone, and hydrazine hydrate.
5. A method for preparing a resistant plastic inner bag material, characterized in that, The preparation steps include the following: (1) Mix tetrabutyl titanate and anhydrous ethanol at a mass ratio of 1:1.44 and stir until homogeneous to obtain solution A; mix acetic acid, double-distilled water and anhydrous ethanol at a mass ratio of 1:1:4.5 and stir until homogeneous to obtain solution B; under stirring at 200 rpm, add solution B dropwise at a mass ratio of 0.85 times that of solution A, react for 40-60 min, add formamide at a mass ratio of 0.08 times that of tetrabutyl titanate and layered tungsten disulfide at a mass ratio of 0.8-1.2 times that of tetrabutyl titanate, stir until homogeneous, and let stand to form a gel; (2) The gel was aged at 40℃ for 24 hours, then soaked twice, filtered, and anhydrous ethanol with a mass of 2 times that of tetrabutyl titanate was added. After standing for 24 hours, it was filtered, dried at room temperature for 24 hours, and then dried at 60℃ for 12 hours to obtain titanium / tungsten particles. The titanium / tungsten particles and urea were mixed at a mass ratio of 1:1 to 1:4, calcined at 500 to 620℃ for 2 hours, and then heated to 800 to 820℃ and calcined for 4 hours to obtain oxygen-rich defect titanium / tungsten particles. Sodium chloropalladium, methanol and water were added. The solution was mixed at a mass ratio of 1:1700 to 1:1800, and the mass ratio of methanol to deionized water in the methanol-water solution was 0.791:
1. The mixture was stirred at 80 rpm for 10 to 15 min to obtain a reaction solution. Oxygen-rich defective titanium / tungsten particles were immersed in the reaction solution at a material-to-liquid ratio of 1:10 to 1:
30. The mixture was irradiated with a 500W xenon lamp for 60 to 180 s, filtered, and dried at 100℃ for 24 h to obtain a composite photocatalyst. The composite photocatalyst was obtained by carboxylation treatment. (3) Mix isoxazole compound, dichloromethane, potassium carbonate, and iodomethane in a mass ratio of 1:15:1.5:0.6 to 1:23:1.5:0.7, stir at 60 to 80 rpm for 10 to 12 hours, extract, wash three times with sodium nitrite standard solution and deionized water, take the organic phase, and dry at 45°C for 10 hours to obtain intermediate D; mix intermediate D, hydrazine hydrate, and ethanol in a mass ratio of 1:6:70 to 1:7:75, stir at 80°C and 80 rpm for 4 to 6 hours, remove by rotary evaporation at -0.07 MPa and 45°C for 3 to 4 hours, extract, wash the organic phase three times with saturated sodium chloride solution, distill at -0.08 MPa and 58°C under reduced pressure for 2 hours, and dry at 70°C for 12 hours to obtain antibacterial agent; (4) Epoxy resin E-51, polyethylene glycol 200, and 1,4-dioxane are mixed in a mass ratio of 15:58:8 to 18:66:
12. After stirring evenly, 0.1 to 0.3 times the mass of epoxy resin E-51 is added to the carboxylated composite photocatalyst. After ultrasonic dispersion at 700 to 900 W for 30 min, 0.01 to 0.08 times the mass of epoxy resin E-51 is added to the antibacterial agent and 0.0003 times the mass of epoxy resin E-51 is added to the dimethylaminopyridine. After stirring evenly, the mixture is poured into a sealed mold and reacted in an 80°C water bath for 8 h. After drying in a 60°C oven for 2 to 4 h, the mixture is freeze-dried at -30°C for 2 to 4 h. The above alternating hot and cold drying is repeated 1 to 3 times to obtain nanoparticles. (5) Polyethylene, nanoparticles, and maleic anhydride-grafted polyethylene are mixed in a mass ratio of 90:10:5 to 90:10:10 and extruded and granulated at 180 to 200°C. The first extruded material is obtained by irradiation. The first extruded material, curing agent D230, calcium carbonate, tributyl citrate, and γ-chloropropyltriethoxysilane are mixed in a mass ratio of 1:0.01:0.05:0.05:0.05 to 1:0.01:0.1:0.1:0.1 and extruded at 200 to 230°C. After cooling for 5 to 10 minutes, the mixture is blown into a film, shaped and cooled, and then cut to obtain antibacterial plastic inner bag material.
6. The method for preparing a resistant plastic inner bag material according to claim 5, characterized in that, The preparation method of layered tungsten disulfide in step (1) is as follows: Sodium tungstate dihydrate is dissolved in ultrapure water at a mass of 80.5 times that of sodium tungstate dihydrate, hydrochloric acid is added until the pH of the solution is 6.5, and L-cysteine solution at a mass of 162 times that of sodium tungstate dihydrate is added. The mass ratio of L-cysteine to deionized water in the L-cysteine solution is 1:
100. After sonication at 400-600W for 10 minutes, the mixture is transferred to a polytetrafluoroethylene-lined stainless steel autoclave and sealed. After heating at 240℃ for 24 hours, it is cooled to room temperature and washed three times by centrifugation at 8000rpm with ultrapure water and ethanol respectively. The precipitate is collected and dried at 80℃ for 24 hours to obtain layered tungsten disulfide.
7. The method for preparing a resistant plastic inner bag material according to claim 5, characterized in that, The soaking process in step (2) is as follows: add 3.2 times the mass of tetrabutyl titanate in anhydrous ethanol, let stand at 60°C for 24 hours, filter, add 3.5 times the mass of tetrabutyl titanate in silicate solution, the mass ratio of tetraethyl orthosilicate to ethanol in the silicate solution is 1:0.84, and let stand at 60°C for 24 hours.
8. The method for preparing a resistant plastic inner bag material according to claim 5, characterized in that, The specific steps of the carboxylation treatment in step (2) are as follows: the composite photocatalyst and anhydrous ethanol are mixed at a mass ratio of 1:16, stirred at 200 rpm for 30-40 min, and then 6.5-10.6 times the mass of the composite photocatalyst in a malonic acid aqueous solution is added. The mass ratio of malonic acid to deionized water in the malonic acid aqueous solution is 1:0.9-1:2.
0. After ultrasonic dispersion at 1600W for 30-40 min, the mixture is stirred at 500 rpm and 60℃ for 4-5 h, then centrifuged at 10000 rpm for 20 min, washed 5 times with anhydrous ethanol, the precipitate is collected, and freeze-dried at -30℃ for 24 h to obtain the carboxylated composite photocatalyst.
9. The method for preparing a resistant plastic inner bag material according to claim 5, characterized in that, The method for preparing the isoxazole compound in step (3) is as follows: A. 4-Bromo-3-mercaptobenzoic acid, vinyl butyl ether, 1,3-bis(diphenylphosphine)propane, palladium acetate, and butanol were mixed in a mass ratio of 1:2.0:0.08:0.03:20 to 1:2.5:0.09:0.03:
24. The mixture was reacted at 100–115 °C for 5–8 h. After cooling to room temperature, hydrochloric acid was added until the pH of the solution was 2. The mixture was extracted, dried with calcium sulfate for 1 h, filtered, and then distilled under reduced pressure at -0.07 MPa and 60 °C for 3–4 h to obtain intermediate A. B. Mix intermediate A, potassium carbonate, sodium laurylate, 4-(hydroxymethyl)-3-vinylacetophenone, and deionized water in a mass ratio of 1:0.9:0.06:1.0:30 to 1:0.9:0.06:1.5:
36. React at 60°C for 4 to 8 hours. Add hydrochloric acid until the pH of the solution is 2. Extract the solution, dry it with calcium sulfate for 1 hour, filter it, and dry it at 80°C for 18 hours to obtain intermediate B. C. Mix intermediate B, triethylamine, and dichloromethane in a mass ratio of 1:0.1:15 to 1:0.3:
22. React at room temperature for 4 to 6 hours, then heat to 45°C and continue reacting for 3 to 5 hours. Add 0.02 to 0.03 times the mass of intermediate B of 4-dimethylaminopyridine and 6 to 10 times the mass of intermediate B of toluene. Heat to 60°C and stir at 80 rpm for 1 to 2 hours. Add 0.4 to 0.5 times the mass of intermediate B of acetic anhydride. React at 60°C for 3 to 5 hours. Add hydrochloric acid until the pH of the solution is 2. Extract, dry with calcium sulfate for 1 hour, filter, and distill under reduced pressure at -0.08 MPa and 68°C for 3 hours to obtain intermediate C. D. Mix intermediate C, toluene, and p-tert-butylcatechol in a mass ratio of 1:6:0.0002 to 1:10:0.0002. React at 90–105 °C for 30 min. Add 0.4–0.5 times the mass of intermediate C to m-methoxystyrene and continue the reaction for 8–10 h. Cool to room temperature and wash twice with a 2% sodium bicarbonate aqueous solution. Add 3–4 times the mass of intermediate C to a 10% hydrochloric acid aqueous solution. Separate the layers. Add sodium hydroxide aqueous solution to the organic phase until the pH of the solution is 10–11. Extract the solution. Distill under reduced pressure at -0.08 MPa and 68 °C for 3 h. Dry at 50 °C for 24 h to obtain the isoxazole compound.
10. The method for preparing a resistant plastic inner bag material according to claim 5, characterized in that, The specific irradiation conditions in step (5) are as follows: 200,000 Curies at a dose rate of 120 Gy / min at room temperature. 60 Irradiation was performed using a Co-γ ray source for 3–5 hours, with an irradiation dose of 12–22 kGy.