High-temperature-resistant plastic bottle for oyster sauce and preparation method thereof

Abstract

The application discloses a high-temperature-resistant plastic bottle for oyster oil and a preparation method thereof, and relates to the technical field of food packaging materials.The high-temperature-resistant plastic bottle for oyster oil comprises the following raw materials in parts by mass: polyethylene terephthalate 70-90 parts; fluorine-modified sodium-based montmorillonite-nano-silicon dioxide composite filler 1-8 parts; hydantoin type antibacterial agent 0.5-5 parts; titanate-modified talc powder 1-8 parts; zinc stearate 0.1-1 part; compatibility agent 0.5-3 parts; and stabilizer 0.1-0.5 part.The high-temperature-resistant plastic bottle for oyster oil prepared by the application has the advantages of high heat resistance, high barrier property, excellent dual-solubility, long-acting antibacterial property and food contact safety.

Description

Technical Field

[0001] This invention relates to the field of food packaging materials technology, specifically to a high-temperature resistant plastic bottle for oyster sauce and its preparation method. Background Technology

[0002] Currently, most commercially available oyster sauce is packaged in polyethylene terephthalate (PET) bottles. However, the heat distortion temperature of ordinary PET is only about 70°C. During sterilization and high-temperature filling, the bottle is prone to shrinkage, deformation, and even breakage. Furthermore, PET has limited barrier properties against oxygen and water vapor, which can easily lead to oxidation, browning, and flavor deterioration of the oyster sauce during long-term storage. In addition, oyster sauce is a typical high-viscosity, multi-component, complex fluid system. The inner wall of ordinary PET bottles has a high surface energy and a strong affinity with oyster sauce, making it very easy for the sauce to "stick" to the bottle. Consumers often need to repeatedly squeeze or rinse the bottle with water to empty the sauce, which not only wastes the product but also makes the remaining sauce prone to oxidation, browning, and the growth of salt-tolerant microorganisms after opening, shortening the shelf life and posing food safety risks.

[0003] In existing technologies, inorganic nanofillers are often added to modify PET bottles to improve their heat resistance and barrier properties. However, inorganic fillers are rich in hydroxyl groups on their surface, which have poor compatibility with the hydrophobic PET matrix and are prone to agglomeration during melt processing. This not only makes it difficult to exert the nano-reinforcing effect but also significantly reduces the tensile strength and transparency of the bottle. To improve anti-adhesion performance, fluorocarbon resin coatings or silicone oil-based slip agents are often used on the inner wall. However, coating processes are costly and prone to peeling off during hot filling or extrusion, failing to meet food contact material safety standards. Furthermore, small-molecule slip agents are prone to migration and precipitation at PET processing temperatures, not only contaminating food but also severely degrading the bottle's mechanical properties and transparency. In addition, oyster sauce is a high-salt, weakly acidic food, and salt-tolerant bacteria easily grow on the inner wall of its packaging. Conventional physical antibacterial methods are insufficient to meet food safety requirements. Therefore, there is an urgent need for a special plastic bottle material for oyster sauce that combines high heat resistance, long-lasting antibacterial properties, good barrier properties, and compliance with food contact safety standards to overcome the shortcomings of existing technologies. Summary of the Invention

[0004] The purpose of this invention is to provide a high-temperature resistant plastic bottle for oyster sauce and its preparation method, thereby solving the following technical problems: Existing polyethylene terephthalate plastic bottles used for oyster sauce packaging have problems such as poor heat resistance, poor barrier properties, and insufficient antibacterial properties.

[0005] The objective of this invention can be achieved through the following technical solutions: A high-temperature resistant plastic bottle for oyster sauce comprises the following raw materials in parts by weight: 70-90 parts of polyethylene terephthalate; 1-8 parts of fluorine-modified sodium montmorillonite-nano silica composite filler; 0.5-5 parts of hydantoin-type antibacterial agent; 1-8 parts of titanate-modified talc; 0.1-1 parts of zinc stearate; 0.5-3 parts of compatibilizer; 0.1-0.5 parts of stabilizer.

[0006] As a further aspect of the present invention: the preparation method of the hydantoin-type antibacterial agent includes at least the following steps: 5,5-Dimethylhydantoin and sodium ethoxide were added to anhydrous ethanol and stirred to react. Then, 2-chloroethyl p-toluenesulfonate was added dropwise and stirred under reflux at 75-78°C for 4-6 hours. After filtration, rotary evaporation, purification and drying, N-(2-hydroxyethyl)-5,5-dimethylhydantoin was obtained. The N-(2-hydroxyethyl)-5,5-dimethylhydantoin and dihydroxyethyl terephthalate were melted and mixed at 130-150°C under nitrogen protection, and then tetraisopropyl titanate was added and the temperature was raised to 180-220°C. The mixture was reacted under reduced pressure for 3-5 hours to remove byproducts. After cooling, purification and drying, hydantoin-type antibacterial agent was obtained.

[0007] As a further aspect of the present invention, the molar ratio of the 5,5-dimethylhydantoin, the sodium ethoxide, and the 2-chloroethyl p-toluenesulfonate is 1:1-1.1:0.8-1.2.

[0008] As a further aspect of the present invention, the molar ratio of N-(2-hydroxyethyl)-5,5-dimethylhydantoin and dihydroxyethyl terephthalate is 1:0.7-1.3.

[0009] As a further aspect of the present invention: the preparation method of the fluorine-modified sodium-based montmorillonite-nano silica composite filler includes at least the following steps: Sodium-based montmorillonite was added to a mixed solution of anhydrous ethanol and ammonia, followed by a mixed solution of tetraethyl orthosilicate and anhydrous ethanol. After hydrolysis, 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise. The mixture was then stirred, centrifuged, washed, and dried to obtain fluorine-modified sodium-based montmorillonite-nano silica composite filler.

[0010] As a further aspect of the present invention: the sodium montmorillonite has a size of 300-500 mesh, and the mass ratio of the sodium montmorillonite, the tetraethyl orthosilicate, and the 1H,1H,2H,2H-perfluorodecyltriethoxysilane is 1:2-5:0.2-0.6.

[0011] As a further aspect of the present invention: the titanate-modified talc powder is obtained by mixing and modifying titanate coupling agent and talc powder at a mass ratio of 1:10-50, and the size of the talc powder is 1000-3000 mesh.

[0012] As a further aspect of the present invention: the compatibilizer is at least one of titanate coupling agents or silane coupling agents, and the stabilizer is one or more of hindered phenolic antioxidants, phosphite auxiliary antioxidants, hydrolytic stabilizers, or ultraviolet absorbers.

[0013] A method for preparing a high-temperature resistant plastic bottle for oyster sauce as described in any of the above claims, comprising at least the following steps: After drying, polyethylene terephthalate is mixed with fluorine-modified sodium montmorillonite-nano silica composite filler, hydantoin-type antibacterial agent, zinc stearate, titanate-modified talc, compatibilizer and stabilizer in a high-speed mixer. Then, it is melt-extruded in a twin-screw extruder, water-cooled and pelletized, injection molded into preforms, and finally blow-molded by a stretch blow molding machine to obtain high-temperature resistant plastic bottles for oyster sauce.

[0014] The beneficial effects of this invention are: This invention provides a high-temperature resistant plastic bottle for oyster sauce. Polyethylene terephthalate (PET) is used as the base resin to provide excellent mechanical strength and processing fluidity. A complex of titanate-modified talc and zinc stearate is added as a highly efficient nucleating agent to promote the refinement of PET crystals, improving heat resistance and crystallization rate. Fluorine-modified sodium montmorillonite-nano silica composite filler is added to construct a micro-nano hierarchical barrier network, giving the bottle excellent dual-repellent properties, significantly reducing the penetration and adsorption of oil and water from oyster sauce to the bottle wall. A hydantoin-type antibacterial agent is added to give the bottle long-lasting broad-spectrum antibacterial function, inhibiting bacterial growth during use. A compatibilizer improves the interfacial bonding between the inorganic filler and the PET matrix, and a stabilizer ensures thermo-oxidative stability during processing and use. The plastic bottle obtained by this invention has excellent high-temperature resistance, oil resistance and impermeability, antibacterial properties, mechanical strength, and food contact safety, and can be widely used in the packaging of high-oil condiments such as oyster sauce, soy sauce, and edible oil.

[0015] The hydantoin-type antibacterial agent prepared in this invention is obtained through a two-step reaction of nucleophilic substitution and transesterification. The molecular structure retains the highly active N-Cl / NH antibacterial hydantoin ring, while simultaneously undergoing in-situ polycondensation with diethyl terephthalate via N-(2-hydroxyethyl) side chains, grafting to form a polyester-type macromolecular antibacterial agent with PET segment end structures. The PET segment structure endows the antibacterial agent with highly matched solubility parameters and thermodynamic compatibility with the matrix resin, allowing it to exist stably in a molecularly dispersed state during melt extrusion. During the biaxial stretch blow molding stage, the antibacterial agent, with its rheological properties and molecular entanglement ability similar to PET, is uniformly dispersed in the amorphous region and inner wall surface of the bottle due to the high orientation of the macromolecular chains. The NH sites of the hydantoin ring are in-situ converted into highly bactericidal N-Cl active structures, continuously releasing trace amounts of hypochlorous acid, achieving broad-spectrum and long-lasting antibacterial effects. Meanwhile, the hydantoin-type antibacterial agent prepared by this invention is covalently anchored to the polymer backbone. The steric hindrance of the macromolecule effectively inhibits the free diffusion of low molecular weight active species. The specific migration amount is far below the safety limit for food contact materials. While ensuring efficient antibacterial activity, it completely avoids the food safety risks caused by chemical migration.

[0016] The fluorine-modified sodium-based montmorillonite-nano silica composite filler of this invention employs a sol-gel method. Sodium-based montmorillonite serves as a layered template, and tetraethyl orthosilicate undergoes hydrolysis and condensation between its layers and on its surface to generate nano-silica particles. The composite particles are then surface-modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. The layered structure of sodium-based montmorillonite provides excellent physical barrier properties, extending the diffusion path of oxygen and water vapor. The in-situ grown nano-silica increases surface roughness and imparts a high specific surface area and reactivity to the filler. The grafting of perfluoroalkyl chains results in extremely low surface energy, giving the material excellent hydrophobic and oleophobic properties, achieving zero wall adhesion, easy drainage, and extremely low residue during oyster sauce pouring / squeezing. The synergistic effect of these three components significantly improves the gas barrier properties, oil resistance, impermeability, and surface self-cleaning ability of PET bottles by adding fluorine-modified sodium montmorillonite-nano silica composite filler. It effectively reduces oyster sauce residue on the bottle walls, and due to its nano-level dispersion and good compatibility with PET, it has little impact on the transparency of the bottle. Detailed Implementation

[0017] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] Example 1: The preparation method of fluorine-modified sodium-based montmorillonite-nano silica composite filler includes the following steps: 10 g of 400-mesh sodium montmorillonite was added to a mixed solution of 120 mL anhydrous ethanol and 15 mL ammonia monohydrate and stirred magnetically for 30 min. Then, a mixed solution containing 20 g tetraethyl orthosilicate and 15 mL anhydrous ethanol was added, and the mixture was stirred at room temperature for 8 h to ensure complete hydrolysis. After complete hydrolysis, 2 g of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise and stirring was continued for 6 h. The mixture was then washed three times by centrifugation with anhydrous ethanol and dried at 60 °C for 12 h to obtain fluorine-modified sodium montmorillonite-nano silica composite filler.

[0019] Example 2: The preparation method of the hydantoin-based antibacterial agent includes the following steps: 14.3 g of 5,5-dimethylhydantoin and 7.0 g of sodium ethoxide were added to 150 mL of anhydrous ethanol and stirred at 78 °C for 30 min. Then, 23.4 g of 2-chloroethyl p-toluenesulfonate was added dropwise and the mixture was refluxed at 78 °C for 5 h. After filtration and rotary evaporation to remove the solvent, the supernatant was extracted by ethyl acetate / water (4:1, v / v). Water was added and the mixture was extracted twice more. Ethyl acetate was removed by rotary evaporation. After drying, the mixture was purified by recrystallization from anhydrous ethanol / n-hexane (9:1, v / v). After drying, N-(2-hydroxyethyl)-5,5-dimethylhydantoin was obtained. After purging 15g of N-(2-hydroxyethyl)-5,5-dimethylhydantoin and 20.3g of dihydroxyethyl terephthalate with nitrogen three times, the mixture was heated to 140℃ and stirred until homogeneous. Then, 0.14g of tetraisopropyl titanate was added, the temperature was raised to 200℃, and the pressure was reduced to -0.09MPa for 4 hours to continuously remove the byproduct ethylene glycol. After the reaction was completed, the mixture was cooled to room temperature, dissolved in anhydrous ethanol, and then slowly poured into 2 times its volume of n-hexane to precipitate. The solid was collected by filtration and vacuum dried to obtain the hydantoin-type antibacterial agent.

[0020] Example 3: The preparation method of titanate-modified talc powder includes the following steps: Add 100g of 1500-mesh talc powder to a high-speed mixer, heat to 105℃, stir and dry at 300r / min for 15min, then add a titanate solution containing 2g of isopropyltris(dioctylpyrophosphoryloxy) titanate and 3g of 15# white oil, mix at 105℃ and 800r / min for 15min, stop heating and cool to room temperature to obtain titanate modified talc powder.

[0021] Example 4: The preparation method of a high-temperature resistant plastic bottle for oyster sauce includes the following steps: 80 parts by weight of polyethylene terephthalate (CR-8864) were dried at 120°C for 6 hours, and then mixed with 3 parts by weight of the fluorine-modified sodium montmorillonite-nano silica composite filler prepared in Example 1, 2 parts by weight of the hydantoin-type antibacterial agent prepared in Example 2, 0.5 parts by weight of zinc stearate, 3 parts by weight of the titanate-modified talc prepared in Example 3, 2 parts by weight of compatibilizer (titanium ester coupling agent, TMC-130), and 0.3 parts by weight of stabilizer (antioxidant 1010) in a high-speed mixer for 10 minutes. The material is then fed into a twin-screw extruder, with temperatures set at 250℃ in zone one, 265℃ in zone two, 275℃ in zone three, and 265℃ in zone four, and a screw speed of 200 rpm. After melt extrusion, it is water-cooled and pelletized, then injection molded into preforms at an injection temperature of 270℃ and a mold temperature of 40℃. Finally, it is heated to 110℃ by a stretch blow molding machine, axially stretched, and blown by high-pressure air to form the preform. It is then heat-set at 140℃ for 25 seconds and cooled to room temperature to obtain a high-temperature resistant plastic bottle for oyster sauce.

[0022] Example 5: The preparation method of a high-temperature resistant plastic bottle for oyster sauce includes the following steps: 85 parts by weight of polyethylene terephthalate (CR-8864) were dried at 120°C for 6 hours, and then mixed with 6 parts by weight of the fluorine-modified sodium montmorillonite-nano silica composite filler prepared in Example 1, 4 parts by weight of the hydantoin-type antibacterial agent prepared in Example 2, 0.7 parts by weight of zinc stearate, 5 parts by weight of the titanate-modified talc prepared in Example 3, 1.5 parts by weight of compatibilizer (titanium ester coupling agent, TMC-130), and 0.4 parts by weight of stabilizer (antioxidant 1010) in a high-speed mixer for 10 hours. The mixture is then fed into a twin-screw extruder, with temperatures set at 250℃ in zone 1, 265℃ in zone 2, 275℃ in zone 3, and 265℃ in zone 4, and a screw speed of 200 rpm. After melt extrusion, it is water-cooled and pelletized, then injection molded into preforms at an injection temperature of 270℃ and a mold temperature of 40℃. Finally, it is heated to 110℃ by a stretch blow molding machine, axially stretched, and blown by high-pressure air to form the preform. It is then heat-set at 140℃ for 25 seconds and cooled to room temperature to obtain a high-temperature resistant plastic bottle for oyster sauce.

[0023] Example 6: The preparation method of a high-temperature resistant plastic bottle for oyster sauce includes the following steps: 75 parts by weight of polyethylene terephthalate (CR-8864) were dried at 120°C for 6 hours, and then mixed with 1.5 parts by weight of the fluorine-modified sodium montmorillonite-nano silica composite filler prepared in Example 1, 2 parts by weight of the hydantoin-type antibacterial agent prepared in Example 2, 0.8 parts by weight of zinc stearate, 7 parts by weight of the titanate-modified talc prepared in Example 3, 2.5 parts by weight of compatibilizer (titanium ester coupling agent, TMC-130), and 0.4 parts by weight of stabilizer (antioxidant 1010) in a high-speed mixer for 1 hour. 0 min, then put into a twin-screw extruder, set the temperature to 250℃ in zone 1, 265℃ in zone 2, 275℃ in zone 3 and 265℃ in zone 4, and the screw speed to 200 rpm. After melt extrusion, it is water-cooled and pelletized, and then injection molded into bottle preforms at an injection temperature of 270℃ and a mold temperature of 40℃. Finally, it is heated to 110℃ by a stretch blow molding machine, axially stretched and blown by high-pressure air to form the preform, and then heat-set at 140℃ for 25s. After cooling to room temperature, a high-temperature resistant plastic bottle for oyster sauce is obtained.

[0024] Comparative Example 1: The preparation method of fluorine-modified sodium-based montmorillonite filler includes the following steps: 10 g of 400-mesh sodium montmorillonite was added to a mixed solution of 120 mL anhydrous ethanol and 15 mL ammonia monohydrate and stirred magnetically for 30 min. Then, 2 g of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise and stirring was continued for 6 h. The mixture was washed three times by centrifugation with anhydrous ethanol (3500 r / min, 10 min) and dried at 60 °C for 12 h to obtain fluorine-modified sodium montmorillonite filler.

[0025] Comparative Example 2: The preparation method of fluorine-modified nano-silica filler includes the following steps: A mixed solution containing 15g tetraethyl orthosilicate and 15mL anhydrous ethanol was adjusted to pH 2-3 with 0.1 mol / L hydrochloric acid. The solution was stirred at room temperature for 8 hours to ensure complete hydrolysis. After complete hydrolysis, 2g of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise and stirring was continued for 6 hours. The solution was washed three times by centrifugation with anhydrous ethanol and dried at 60℃ for 12 hours to obtain fluorine-modified nano-silica filler.

[0026] Comparative Example 3: The preparation method of sodium-based montmorillonite-nano silica composite filler includes the following steps: 10 g of 400-mesh sodium montmorillonite was added to a mixed solution of 120 mL anhydrous ethanol and 15 mL ammonia monohydrate and stirred magnetically for 30 min. Then, a mixed solution containing 15 g tetraethyl orthosilicate and 15 mL anhydrous ethanol was added, and the mixture was stirred at room temperature for 8 h to ensure complete hydrolysis. After complete hydrolysis, the mixture was washed three times with anhydrous ethanol by centrifugation and dried at 60 °C for 12 h to obtain sodium montmorillonite-nano silica composite filler. Compared with Example 4, Comparative Example 4 only replaced the fluorine-modified sodium montmorillonite-nano silica composite filler prepared in Example 1 with the fluorine-modified sodium montmorillonite filler prepared in Comparative Example 1 by the same mass. The remaining components and preparation methods were completely the same as those in Example 4.

[0027] Compared with Example 4, Comparative Example 5 only replaced the fluorine-modified sodium montmorillonite-nano silica composite filler prepared in Example 1 with a physical mixture of fluorine-modified sodium montmorillonite filler prepared in Comparative Example 1 and fluorine-modified nano silica filler prepared in Comparative Example 2. The remaining components and preparation methods were completely the same as those in Example 4.

[0028] Compared with Example 4, Comparative Example 6 only replaced the fluorine-modified sodium montmorillonite-nano silica composite filler prepared in Example 1 with the sodium montmorillonite-nano silica composite filler prepared in Comparative Example 3 by the same mass. The remaining components and preparation methods were completely the same as those in Example 4.

[0029] Compared with Example 4, Comparative Example 7 only replaced the hydantoin-type antibacterial agent prepared in Example 2 with N-(2-hydroxyethyl)-5,5-dimethylhydantoin prepared in Example 2 by the same mass. The remaining components and preparation methods were completely consistent with Example 4.

[0030] Compared with Example 4, Comparative Example 8 only omits the fluorine-modified sodium-based montmorillonite-nano silica composite filler prepared in Example 1; the remaining components and preparation methods are completely the same as in Example 4. Compared with Example 4, Comparative Example 9 only did not add the hydantoin-type antibacterial agent prepared in Example 2; the other components and preparation methods were completely the same as in Example 4.

[0031] Compared with Example 4, Comparative Example 10 only did not add the titanate-modified talc powder prepared in Example 3, while the other components and preparation methods were completely the same as those in Example 4.

[0032] Performance testing Notched impact strength test: The notched impact strength of the plastic bottle was tested according to GB / T1043.1-2024 "Determination of impact performance of simply supported beams - Part 1: Non-instrumental impact test"; the test results are shown in Table 1. Barrier performance test: According to GB / T1038-2022 "Test method for gas permeability of plastic films and sheets - differential pressure method", the oxygen permeability of plastic bottles at a relative humidity of 60% was tested; the test results are shown in Table 1. Transmittance performance test: The transmittance of the plastic bottle was tested according to GB / T2410-2024 "Determination of transmittance and haze of transparent plastics"; the test results are shown in Table 1. Heat shrinkage rate test: According to GB / T 17931-2023 "Polyethylene terephthalate (PET) resin for bottles", the bottle was immersed in a 90℃ constant temperature water bath for 30 minutes, and after cooling, the heat shrinkage rate of the bottle diameter was tested; the test results are shown in Table 1; Total migration test: According to GB 4806.7-2023 "National Food Safety Standard for Plastic Materials and Products for Food Contact", 4% acetic acid (volume fraction) was used as a simulation solution, and the plastic bottles were immersed at 60℃ for 10 days to test the total migration; the test results are shown in Table 1. Table 1: Statistical Table of Performance Test Data for Plastic Bottles in Examples 4-6 and Comparative Examples 4-10 As shown in Table 1, the oyster sauce plastic bottle prepared by this invention maintains high light transmittance while significantly improving notched impact strength, reducing oxygen permeability, minimizing 90°C thermal shrinkage, and ensuring total migration is far below food safety limits. Comparative Example 4 used only fluorinated montmorillonite as filler, resulting in a discontinuous barrier network and increased oxygen permeability. Comparative Example 5 used physically blended filler, leading to poor interfacial compatibility, stress concentration, and reduced impact strength. Comparative Example 6 used unfluorinated filler, resulting in a sharp drop in contact angle, demonstrating that fluorosilane grafting is the core of constructing a double-hydrophobic interface. Comparative Example 7 added only intermediates, resulting in a lack of macromolecular polyester structure, leading to decreased compatibility and thermal stability, a significant increase in migration, and a substantial decrease in antibacterial effect. Comparative Example 8 did not add fluorinated composite filler, resulting in a precipitous drop in barrier properties, heat resistance, and anti-wall adhesion performance. Comparative Example 9 did not add hydantoin-type antibacterial agents, completely losing long-lasting antibacterial properties. Comparative Example 10 did not add titanate-modified talc, resulting in insufficient nucleation effect, low crystallinity, significantly reduced heat resistance, and a significantly increased thermal shrinkage rate.

[0033] Antibacterial test: Tested according to QB / T2591-2023, using Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC6538) for 24 hours; test results are shown in Table 2. Contact angle test: According to GB / T 30693-2024 "Determination of contact angle of plastic film and sheet", the static contact angle of the inner wall of the plastic bottle with deionized water and diiodomethane was determined by the seat drop method, and the oil phase contact angle was converted; the test results are shown in Table 2; Table 2: Statistical Table of Performance Test Data for Plastic Bottles in Examples 4-6 and Comparative Examples 4-10 As shown in Table 2, the inner wall of the oyster sauce bottle prepared by this invention exhibits excellent dual-repellent properties and long-lasting antibacterial activity. This indicates that the fluorinated modified filler successfully accumulates on the inner wall during the blow molding and stretching process, forming a stable micro-nano rough low-energy surface, achieving zero wall adhesion when pouring oyster sauce. Furthermore, antibacterial tests show that the inactivation rates of Escherichia coli and Staphylococcus aureus are both ≥99.9%.

[0034] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0035] The foregoing has provided a detailed description of one embodiment of the present invention, but this description is merely a preferred embodiment and should not be construed as limiting the scope of the invention. All equivalent variations and modifications made within the scope of the claims of this invention should still fall within the patent coverage of this invention.

Claims

1. A high-temperature-resistant plastic bottle for oyster sauce, characterized by comprising: Includes the following quantities of raw materials: 70-90 parts of polyethylene terephthalate; 1-8 parts of fluorine-modified sodium montmorillonite-nano silica composite filler; 0.5-5 parts of hydantoin-type antibacterial agent; 1-8 parts of titanate-modified talc; 0.1-1 parts of zinc stearate; 0.5-3 parts of compatibilizer; 0.1-0.5 parts of stabilizer.

2. The high-temperature-resistant plastic bottle for oyster sauce according to claim 1, characterized in that, The preparation method of the hydantoin-based antibacterial agent includes at least the following steps: 5,5-Dimethylhydantoin and sodium ethoxide were added to anhydrous ethanol and stirred to react. Then, 2-chloroethyl p-toluenesulfonate was added dropwise and refluxed. After filtration, rotary evaporation, purification and drying, N-(2-hydroxyethyl)-5,5-dimethylhydantoin was obtained. The N-(2-hydroxyethyl)-5,5-dimethylhydantoin and dihydroxyethyl terephthalate were melt-mixed under nitrogen protection, and then tetraisopropyl titanate was added to react and remove the byproducts. After cooling, purification and drying, hydantoin-type antibacterial agent was obtained.

3. The high-temperature-resistant plastic bottle for oyster sauce according to claim 2, characterized in that, The molar ratio of the 5,5-dimethylhydantoin, the sodium ethoxide, and the 2-chloroethyl p-toluenesulfonate is 1:1-1.1:0.8-1.

2.

4. The high-temperature-resistant plastic bottle for oyster sauce according to claim 2, characterized in that, The molar ratio of N-(2-hydroxyethyl)-5,5-dimethylhydantoin to dihydroxyethyl terephthalate is 1:0.7-1.

3.

5. The high-temperature-resistant plastic bottle for oyster sauce according to claim 1, characterized in that, The preparation method of the fluorine-modified sodium-based montmorillonite-nano silica composite filler includes at least the following steps: Sodium-based montmorillonite was added to a mixed solution of anhydrous ethanol and ammonia, followed by a mixed solution of tetraethyl orthosilicate and anhydrous ethanol. After hydrolysis, 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise. The mixture was then stirred, centrifuged, washed, and dried to obtain fluorine-modified sodium-based montmorillonite-nano silica composite filler.

6. The high-temperature-resistant plastic bottle for oyster sauce according to claim 5, characterized in that, The sodium montmorillonite has a mesh size of 300-500, and the mass ratio of the sodium montmorillonite, the tetraethyl orthosilicate, and the 1H,1H,2H,2H-perfluorodecyltriethoxysilane is 1:2-5:0.2-0.

6.

7. The high-temperature-resistant plastic bottle for oyster sauce according to claim 1, characterized in that, The titanate-modified talc powder is obtained by mixing and modifying titanate coupling agent and talc powder at a mass ratio of 1:10-50, and the size of the talc powder is 1000-3000 mesh.

8. A high-temperature resistant plastic bottle for oyster sauce according to claim 1, characterized in that, The compatibilizer is at least one of titanate coupling agents or silane coupling agents, and the stabilizer is one or more of hindered phenolic antioxidants, phosphite auxiliary antioxidants, hydrolytic stabilizers, or ultraviolet absorbers.

9. A method for preparing a high-temperature resistant plastic bottle for oyster sauce according to any one of claims 1-8, characterized in that, At least the following steps are included: After drying, polyethylene terephthalate is mixed with fluorine-modified sodium montmorillonite-nano silica composite filler, hydantoin-type antibacterial agent, zinc stearate, titanate-modified talc, compatibilizer and stabilizer in a high-speed mixer. Then, it is melt-extruded in a twin-screw extruder, water-cooled and pelletized, injection molded into preforms, and finally blow-molded by a stretch blow molding machine to obtain high-temperature resistant plastic bottles for oyster sauce.

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