Modified pcr polyester plastic water cup and preparation method thereof

Abstract

The application discloses a modified PCT polyester plastic water cup and a preparation method thereof, and relates to the technical field of tableware, wherein the raw materials include 87.5-93% Tritan copolyester, 0.5-1.5% silane modified graphene loaded silver nanoparticles, 1-2.5% modified zinc oxide / silver nano composite particles, 0.5-1% dispersant, 0.2-0.5% antioxidant, 3-6% toughening agent and 0.5-1% lubricant according to mass percentage. The modified PCT polyester plastic water cup has excellent antibacterial property and impact strength.

Description

Technical Field

[0001] This application relates to the field of catering utensils technology, and in particular to a modified PCT polyester plastic water cup and its preparation method. Background Technology

[0002] Plastic water cups are widely used drinking utensils in daily life, and their material safety, antibacterial properties, and durability have always been core concerns for consumers and manufacturers. Polycyclohexanediol terephthalate (PCT) and its modified copolyesters (such as Tritan) have become important choices in the field of food contact materials due to their excellent transparency, impact resistance, and chemical corrosion resistance, and the absence of harmful substances such as bisphenol A, gradually replacing traditional materials such as polycarbonate (PC) and bisphenol A-type epoxy resins. However, plastic water cups easily retain moisture and organic matter during use, providing favorable conditions for bacterial growth. Conventional plastic surfaces are insufficient to inhibit the adhesion and reproduction of common pathogenic bacteria such as Escherichia coli and Staphylococcus aureus, posing potential hygiene and safety hazards with long-term use.

[0003] To impart antibacterial properties to plastic materials, current technologies typically employ the addition of inorganic or organic antibacterial agents. Inorganic antibacterial agents are primarily silver-based, zinc-based, and copper-based metals and their compounds. Nano-silver is particularly favored due to its broad-spectrum antibacterial properties, high efficiency, and low toxicity. However, nano-silver particles have a large specific surface area and high surface energy, making them prone to aggregation. This leads to uneven dispersion within the polymer matrix, reducing antibacterial efficiency and affecting the material's transparency and mechanical properties. Zinc oxide, as a safe and non-toxic semiconductor material, also possesses good antibacterial activity and UV shielding capabilities. However, its antibacterial effect is limited when used alone, and its interfacial compatibility with the polymer matrix is ​​poor. The insufficient interfacial bonding between nanoparticles and the matrix resin makes it prone to becoming stress concentration points under stress, leading to increased material brittleness. Summary of the Invention

[0004] In order to provide a plastic water cup material with excellent antibacterial properties, this application provides a modified PCT polyester plastic water cup and its preparation method.

[0005] This application provides a modified PCT polyester plastic water cup, which adopts the following technical solution: A modified PCT polyester plastic water cup, the raw materials by mass percentage include 87.5-93% Tritan copolyester, 0.5-1.5% silane-modified graphene-supported silver nanoparticles, 1-2.5% modified zinc oxide / silver nanocomposite particles, 0.5-1% dispersant, 0.2-0.5% antioxidant, 3-6% toughening agent, and 0.5-1% lubricant.

[0006] Preferably, the raw materials comprise, by weight percentage, 91% Tritan copolyester, 1% silane-modified graphene-supported silver nanoparticles, 1.5% modified zinc oxide / silver nanocomposite particles, 0.8% dispersant, 0.4% antioxidant, 4.5% toughening agent, and 0.8% lubricant.

[0007] Preferably, the silane-modified graphene-supported silver nanoparticles are prepared from the following raw materials in parts by weight: 0.4-0.6 parts graphene oxide powder, 300-450 parts ethanol, 125-185 parts deionized water, 0.8-1.2 parts silane coupling agent KH570, and 0.2-0.3 parts silver nitrate.

[0008] Preferably, the method for preparing the silane-modified graphene-supported silver nanoparticles includes the following steps: S1. Add 0.4-0.6 parts of graphene oxide powder to a mixed solvent of 300-450 parts of ethanol and 100-150 parts of deionized water, and sonicate for 30-60 minutes to obtain a graphene oxide dispersion. S2. Add 0.8-1.2 parts of silane coupling agent KH570 to the graphene oxide dispersion, stir evenly, adjust the pH of the mixed solution to 8-9, and then stir at 60-70℃ for 12-16h to obtain the initial dispersion. S3. Dissolve 0.2-0.3 parts of silver nitrate in 25-35 parts of deionized water, adjust the pH of the solution to 9-10, and stir until completely dissolved to obtain a silver ion solution; add the silver ion solution to the initial dispersion, and stir at room temperature and a stirring speed of 600-700 rpm for 1-2 hours to allow the reaction to occur; after the reaction is complete, centrifuge the mixed dispersion for 10-15 minutes, remove the supernatant, wash the precipitate with distilled water, and centrifuge again. Repeat the operation several times, and freeze-dry the precipitate for 48-60 hours to obtain silane-modified graphene-supported silver nanoparticles.

[0009] Preferably, the modified zinc oxide / silver nanocomposite particles are prepared from the following raw materials in parts by weight: 1-2 parts zinc oxide / silver nanocomposite particles, 60-120 parts anhydrous ethanol, and 2-4 parts phenyltriethoxysilane.

[0010] Preferably, the zinc oxide / silver nanocomposite particles are prepared from the following raw materials in parts by weight: 0.1-0.15 parts anhydrous stannous chloride, 100-150 parts hydrochloric acid solution, 0.4-0.6 parts nano zinc oxide, 100-150 parts deionized water, 200-300 parts silver ammonia solution, and 0.5-0.8 parts formaldehyde in an ethanol aqueous solution.

[0011] Preferably, the method for preparing the zinc oxide / silver nanocomposite particles includes the following steps: Dissolve 0.1-0.15 parts of anhydrous stannous chloride in 100-150 parts of hydrochloric acid solution; then add 0.4-0.6 parts of nano-zinc oxide, and stir continuously at room temperature for 30-50 min. Centrifuge to recover the precipitate, then wash several times with water. Disperse the precipitate in 100-150 parts of deionized water to obtain an activation solution of nano-zinc oxide-stannous ion complex; add 100-150 parts of silver ammonia solution to the activation solution, stir for 30-40 min, and filter to obtain nano-zinc oxide-silver active species; disperse the nano-zinc oxide-silver active species in 100-150 parts of silver ammonia solution and stir evenly, then add 0.5-0.8 parts of formaldehyde in ethanol aqueous solution; stir again for 30-40 min, then filter and rinse with ultrapure water; finally, vacuum dry at 50-60℃ for 24-30 h to obtain zinc oxide / silver nanocomposite particles.

[0012] Preferably, the preparation method of the modified zinc oxide / silver nanocomposite particles includes the following steps: Add 1-2 parts of zinc oxide / silver nanocomposite particles to 60-120 parts of anhydrous ethanol, adjust the pH of the solution to 8-9, and ultrasonically disperse for 30-40 min; then add 2-4 parts of phenyltriethoxysilane, and ultrasonically disperse again for 30-40 min; finally, heat and stir the resulting mixture in an oil bath at 50-60℃ for 24-30 h; after the reaction is completed, centrifuge the obtained powder, wash it several times with anhydrous ethanol, and finally vacuum dry it at 50-60℃ for 24-30 h to obtain modified zinc oxide / silver nanocomposite particles.

[0013] This application provides a method for preparing a modified PCT polyester plastic water cup, which adopts the following technical solution: A method for preparing a modified PCT polyester plastic water cup includes the following steps: S1. Weigh the Tritan copolyester, silane-modified graphene-supported silver nanoparticles, modified zinc oxide / silver nanocomposite particles, dispersant, antioxidant, toughening agent, and lubricant by mass percentage; place the Tritan copolyester and toughening agent in a vacuum drying oven and dry at 100-110℃ for 4-6 hours; Add the above raw materials to a high-speed mixer and mix at 1000-1500 rpm for 10-15 minutes to obtain a premix. S2. Add the premixed material to the extruder for melt extrusion. After extrusion, cool and granulate to obtain masterbatch. Place the masterbatch in a vacuum drying oven and dry at 100-110℃ for 4-6 hours. Add the dried masterbatch to the injection molding machine to injection mold into water cup products. After the molded products are cooled and demolded, place them in an oven at 80-90℃ for 2-4 hours and then slowly cool to room temperature to obtain modified PCT polyester plastic water cups.

[0014] Preferably, the temperatures of each section of the extruder are set as follows: Zone 1 240-250℃, Zone 2 245-255℃, Zone 3 250-260℃, Zone 4 255-265℃, Zone 5 265-275℃, and Die Head 270-280℃; the screw speed is controlled at 100-200 rpm.

[0015] In summary, this application includes at least one of the following beneficial technical effects: 1. This application utilizes the high specific surface area and excellent adsorption properties of graphene to load silver nanoparticles, while simultaneously leveraging the composite effect of zinc oxide and silver to generate a synergistic antibacterial effect. After surface modification with a silane coupling agent, the two types of nanoparticles exhibit good interfacial compatibility with the Tritan matrix. This not only ensures the uniform dispersion and long-term stability of the antibacterial components in the polymer matrix, but also avoids the problems of easy aggregation and low antibacterial efficiency of single antibacterial agents, thus enabling the water cup to possess long-lasting and highly effective broad-spectrum antibacterial properties. Detailed Implementation

[0016] The present application will be further described in detail below with reference to the embodiments.

[0017] The chemical reagents used in the preparation examples, embodiments, and comparative examples provided in this invention are all commercially available products, and their brands and manufacturers are as follows: Tritan copolyester, Shanghai Bangsu New Materials Co., Ltd.; BYK-161 dispersant, Guangdong Wengjiang Chemical Reagent Co., Ltd.; Antioxidant 1010, Shanghai Maclean Biochemical Technology Co., Ltd., Product No.: P750268; Antioxidant 168, Shanghai Maclean Biochemical Technology Co., Ltd., Product No.: T822863; Maleic anhydride grafted with POE, Nanjing Feiteng New Material Technology Co., Ltd.; N,N'-Ethylenebis-stearamide, Shanghai Yuanye Biotechnology Co., Ltd., Product No.: S60452; Zinc stearate, Shanghai Maclean Biochemical Technology Co., Ltd., Product No.: Z820684.

[0018] Preparation Example 1: Preparation of Silane-Modified Graphene-Supported Silver Nanoparticles Preparation Example 1.1 S1. Add 0.4g of graphene oxide powder to a mixed solvent of 300g of ethanol and 100g of deionized water, and sonicate for 30min to obtain a graphene oxide dispersion. S2. Add 0.8g of silane coupling agent KH570 to the graphene oxide dispersion, stir evenly, adjust the pH of the mixed solution to 8 with 10% ammonia water, and then stir at 60℃ for 12h to obtain the initial dispersion. S3. Dissolve 0.2g of silver nitrate in 25g of deionized water, adjust the pH of the solution to 9 with 10% ammonia, and stir until completely dissolved to obtain a silver ion solution. Add the silver ion solution to the initial dispersion and stir at room temperature and 600rpm for 1h to allow the reaction to occur. After the reaction is complete, centrifuge the mixed dispersion for 10min, remove the supernatant, wash the precipitate with distilled water, and centrifuge again. Repeat the operation twice, and freeze-dry the precipitate for 48h to obtain silane-modified graphene-supported silver nanoparticles.

[0019] Preparation Example 1.2 S1. Add 0.5g of graphene oxide powder to a mixed solvent of 375g of ethanol and 125g of deionized water, and sonicate for 45min to obtain a graphene oxide dispersion. S2. Add 1g of silane coupling agent KH570 to the graphene oxide dispersion, stir evenly, adjust the pH of the mixed solution to 8.5 with 10% ammonia water, and then stir at 65℃ for 14h to obtain the initial dispersion. S3. Dissolve 0.25g of silver nitrate in 30g of deionized water, adjust the pH of the solution to 9.5 with 10% ammonia, and stir until completely dissolved to obtain a silver ion solution. Add the silver ion solution to the initial dispersion and stir at room temperature and 650rpm for 1.5h to allow the reaction to occur. After the reaction is complete, centrifuge the mixed dispersion for 13min, remove the supernatant, wash the precipitate with distilled water, and centrifuge again. Repeat the operation 3 times, and freeze-dry the precipitate for 54h to obtain silane-modified graphene-supported silver nanoparticles.

[0020] Preparation Example 1.3 S1. Add 0.6g of graphene oxide powder to a mixed solvent of 450g of ethanol and 150g of deionized water, and sonicate for 60min to obtain a graphene oxide dispersion. S2. Add 1.2g of silane coupling agent KH570 to the graphene oxide dispersion, stir evenly, adjust the pH of the mixed solution to 9 with 10% ammonia water, and then stir at 70℃ for 16h to obtain the initial dispersion. S3. Dissolve 0.3g of silver nitrate in 35g of deionized water, adjust the pH of the solution to 10 with 10% ammonia, and stir until completely dissolved to obtain a silver ion solution. Add the silver ion solution to the initial dispersion and stir at room temperature and 700rpm for 2h to allow the reaction to occur. After the reaction is complete, centrifuge the mixed dispersion for 15min, remove the supernatant, wash the precipitate with distilled water, and centrifuge again. Repeat the operation 4 times, and freeze-dry the precipitate for 60h to obtain silane-modified graphene-supported silver nanoparticles.

[0021] Preparation Example 2: Preparation of Modified Zinc Oxide / Silver Nanocomposite Particles Preparation Example 2.1 S1. Dissolve 0.1 g of anhydrous stannous chloride in 100 g of 0.01 mol / L hydrochloric acid solution; then add 0.4 g of nano-zinc oxide, and stir continuously for 30 min at room temperature. Centrifuge to recover the precipitate, then wash three times with water. The precipitate is then dispersed in 100 g of deionized water to obtain an activation solution of nano-zinc oxide-stannous ion complex; add 100 g of 0.01 mol / L silver ammonia solution to the activation solution, stir for 30 min, and filter to obtain nano-zinc oxide-silver active seeds; disperse the nano-zinc oxide-silver active seeds in 100 g of 0.01 mol / L silver ammonia solution and stir evenly, then add 0.5 g of formaldehyde in an ethanol aqueous solution (formaldehyde:deionized water:anhydrous ethanol volume ratio 1:1:23); stir for another 30 min, then filter and rinse with ultrapure water; finally, vacuum dry at 50 °C for 24 h to obtain zinc oxide / silver nanocomposite particles. S2. Add 1g of zinc oxide / silver nanocomposite particles to 60g of anhydrous ethanol, and adjust the pH of the solution to 8 with 10% ammonia water. Disperse the mixture by sonication for 30min. Then add 2g of phenyltriethoxysilane and disperse by sonication again for 30min. Finally, heat and stir the resulting mixture in an oil bath at 50℃ for 24h. After the reaction is completed, centrifuge the powder obtained, wash it three times with anhydrous ethanol, and finally vacuum dry it at 50℃ for 24h to obtain modified zinc oxide / silver nanocomposite particles.

[0022] Preparation Example 2.2 S1. Dissolve 0.125 g of anhydrous stannous chloride in 125 g of 0.01 mol / L hydrochloric acid solution; then add 0.5 g of nano-zinc oxide, and stir continuously at room temperature for 40 min. Centrifuge to recover the precipitate, then wash with water four times. The precipitate is then dispersed in 125 g of deionized water to obtain an activation solution of nano-zinc oxide-stannous ion complex; add 125 g of 0.01 mol / L silver ammonia solution to the activation solution, stir for 35 min, and filter to obtain nano-zinc oxide-silver active seeds; disperse the nano-zinc oxide-silver active seeds in 125 g of 0.01 mol / L silver ammonia solution and stir evenly, then add 0.65 g of formaldehyde in an ethanol aqueous solution (formaldehyde:deionized water:anhydrous ethanol volume ratio 1:1:23); stir for another 35 min, then filter and rinse with ultrapure water; finally, vacuum dry at 55 °C for 27 h to obtain zinc oxide / silver nanocomposite particles. S2. Add 1.5g of zinc oxide / silver nanocomposite particles to 90g of anhydrous ethanol, and adjust the pH of the solution to 8.5 with 10% ammonia water. Disperse the mixture by sonication for 35min. Then add 3g of phenyltriethoxysilane and disperse by sonication again for 35min. Finally, heat and stir the resulting mixture in an oil bath at 55℃ for 27h. After the reaction is completed, centrifuge the powder obtained, wash it 4 times with anhydrous ethanol, and finally vacuum dry it at 55℃ for 27h to obtain the modified zinc oxide / silver nanocomposite particles.

[0023] Preparation Example 2.3 S1. Dissolve 0.15 g of anhydrous stannous chloride in 150 g of 0.01 mol / L hydrochloric acid solution; then add 0.6 g of nano-zinc oxide, and stir continuously at room temperature for 50 min. Centrifuge to recover the precipitate, then wash with water 5 times. The precipitate is then dispersed in 150 g of deionized water to obtain an activation solution of nano-zinc oxide-stannous ion complex; add 150 g of 0.01 mol / L silver ammonia solution to the activation solution, stir for 40 min, and filter to obtain nano-zinc oxide-silver active seeds; disperse the nano-zinc oxide-silver active seeds in 150 g of 0.01 mol / L silver ammonia solution and stir evenly, then add 0.8 g of formaldehyde in an ethanol aqueous solution (the volume ratio of formaldehyde:deionized water:anhydrous ethanol is 1:1:23); stir for another 40 min, then filter and rinse with ultrapure water; finally, vacuum dry at 60 °C for 30 h to obtain zinc oxide / silver nanocomposite particles. S2. Add 2g of zinc oxide / silver nanocomposite particles to 120g of anhydrous ethanol, and adjust the pH of the solution to 9 with 10% ammonia water. Disperse the mixture by sonication for 40min. Then add 4g of phenyltriethoxysilane and disperse by sonication again for 40min. Finally, heat and stir the resulting mixture in an oil bath at 60℃ for 30h. After the reaction is completed, centrifuge the powder obtained, wash it 5 times with anhydrous ethanol, and finally vacuum dry it at 60℃ for 30h to obtain modified zinc oxide / silver nanocomposite particles.

[0024] Example 1 S1. Weigh 87.5g of Tritan copolyester, 1.5g of silane-modified graphene-supported silver nanoparticles prepared in Preparation Example 1.1, 2.5g of modified zinc oxide / silver nanocomposite particles prepared in Preparation Example 2.1, 1g of dispersant, 0.5g of antioxidant, 6g of toughening agent, and 1g of lubricant; place the Tritan copolyester and toughening agent in a vacuum drying oven and dry at 100°C for 4 hours; Add the above raw materials to a high-speed mixer and mix at 1000 rpm for 10 minutes to obtain a premix. S2. The premixed material is added to an extruder for melt extrusion. After extrusion, it is cooled and granulated to obtain masterbatch. The masterbatch is placed in a vacuum drying oven and dried at 100°C for 4 hours. The dried masterbatch is added to an injection molding machine for injection molding into water cup products. After the molded products are cooled and demolded, they are placed in an oven at 80°C for 2 hours and then slowly cooled to room temperature to obtain modified PCT polyester plastic water cups. The dispersant used in this embodiment is BYK-161 dispersant; the antioxidant used is a complex of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1; the toughening agent used is maleic anhydride-grafted POE; and the lubricant used is a complex of zinc stearate and N,N'-ethylene bis-stearamide in a mass ratio of 1:1.5. In this embodiment, the temperatures of each section of the extruder are set as follows: Zone 1 240℃, Zone 2 245℃, Zone 3 250℃, Zone 4 255℃, Zone 5 265℃, and Die Head 270℃; the screw speed is controlled at 100 rpm.

[0025] Example 2 S1. Weigh 91g of Tritan copolyester, 1g of silane-modified graphene-supported silver nanoparticles prepared in Preparation Example 1.1, 1.5g of modified zinc oxide / silver nanocomposite particles prepared in Preparation Example 2.1, 0.8g of dispersant, 0.4g of antioxidant, 4.5g of toughening agent, and 0.8g of lubricant; place the Tritan copolyester and toughening agent in a vacuum drying oven and dry at 100°C for 4 hours; Add the above raw materials to a high-speed mixer and mix at 1000 rpm for 10 minutes to obtain a premix. S2. The premixed material is added to an extruder for melt extrusion. After extrusion, it is cooled and granulated to obtain masterbatch. The masterbatch is placed in a vacuum drying oven and dried at 100°C for 4 hours. The dried masterbatch is added to an injection molding machine for injection molding into water cup products. After the molded products are cooled and demolded, they are placed in an oven at 80°C for 2 hours and then slowly cooled to room temperature to obtain modified PCT polyester plastic water cups. The dispersant used in this embodiment is BYK-161 dispersant; the antioxidant used is a complex of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1; the toughening agent used is maleic anhydride-grafted POE; and the lubricant used is a complex of zinc stearate and N,N'-ethylene bis-stearamide in a mass ratio of 1:1.5. In this embodiment, the temperatures of each section of the extruder are set as follows: Zone 1 240℃, Zone 2 245℃, Zone 3 250℃, Zone 4 255℃, Zone 5 265℃, and Die Head 270℃; the screw speed is controlled at 100 rpm.

[0026] Example 3 S1. Weigh 93g of Tritan copolyester, 0.5g of silane-modified graphene-supported silver nanoparticles prepared in Preparation Example 1.1, 1g of modified zinc oxide / silver nanocomposite particles prepared in Preparation Example 2.1, 0.5g of dispersant, 0.3g of antioxidant, 4g of toughening agent, and 0.7g of lubricant; place the Tritan copolyester and toughening agent in a vacuum drying oven and dry at 100°C for 4 hours; Add the above raw materials to a high-speed mixer and mix at 1000 rpm for 10 minutes to obtain a premix. S2. The premixed material is added to an extruder for melt extrusion. After extrusion, it is cooled and granulated to obtain masterbatch. The masterbatch is placed in a vacuum drying oven and dried at 100°C for 4 hours. The dried masterbatch is added to an injection molding machine for injection molding into water cup products. After the molded products are cooled and demolded, they are placed in an oven at 80°C for 2 hours and then slowly cooled to room temperature to obtain modified PCT polyester plastic water cups. The dispersant used in this embodiment is BYK-161 dispersant; the antioxidant used is a complex of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1; the toughening agent used is maleic anhydride-grafted POE; and the lubricant used is a complex of zinc stearate and N,N'-ethylene bis-stearamide in a mass ratio of 1:1.5. In this embodiment, the temperatures of each section of the extruder are set as follows: Zone 1 240℃, Zone 2 245℃, Zone 3 250℃, Zone 4 255℃, Zone 5 265℃, and Die Head 270℃; the screw speed is controlled at 100 rpm.

[0027] Example 4 S1. Weigh 85g of Tritan copolyester, 1.5g of silane-modified graphene-supported silver nanoparticles prepared in Preparation Example 1.2, 2.5g of modified zinc oxide / silver nanocomposite particles prepared in Preparation Example 2.2, 1g of dispersant, 0.5g of antioxidant, 6g of toughening agent, and 1g of lubricant; place the Tritan copolyester and toughening agent in a vacuum drying oven and dry at 105°C for 5 hours; The above raw materials were added to a high-speed mixer and mixed at 1250 rpm for 13 minutes to obtain a premix. S2. The premixed material is added to an extruder for melt extrusion. After extrusion, it is cooled and granulated to obtain masterbatch. The masterbatch is placed in a vacuum drying oven and dried at 105℃ for 5 hours. The dried masterbatch is added to an injection molding machine for injection molding into water cup products. After the molded products are cooled and demolded, they are placed in an oven at 85℃ for 3 hours and then slowly cooled to room temperature to obtain modified PCT polyester plastic water cups. The dispersant used in this embodiment is BYK-161 dispersant; the antioxidant used is a complex of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1; the toughening agent used is maleic anhydride-grafted POE; and the lubricant used is a complex of zinc stearate and N,N'-ethylene bis-stearamide in a mass ratio of 1:1.5. In this embodiment, the temperatures of each section of the extruder are set as follows: Zone 1 245℃, Zone 2 250℃, Zone 3 255℃, Zone 4 260℃, Zone 5 270℃, and Die Head 275℃; the screw speed is controlled at 150 rpm.

[0028] Example 5 S1. Weigh 85g of Tritan copolyester, 1.5g of silane-modified graphene-supported silver nanoparticles prepared in Preparation Example 1.3, 2.5g of modified zinc oxide / silver nanocomposite particles prepared in Preparation Example 2.3, 1g of dispersant, 0.5g of antioxidant, 6g of toughening agent, and 1g of lubricant; place the Tritan copolyester and toughening agent in a vacuum drying oven and dry at 110°C for 6 hours; The above raw materials were added to a high-speed mixer and mixed at 1500 rpm for 15 minutes to obtain a premix. S2. The premixed material is added to an extruder for melt extrusion. After extrusion, it is cooled and granulated to obtain masterbatch. The masterbatch is placed in a vacuum drying oven and dried at 110°C for 6 hours. The dried masterbatch is added to an injection molding machine to be injection molded into a water cup product. After the molded product is cooled and demolded, it is placed in an oven at 90°C for 4 hours and then slowly cooled to room temperature to obtain a modified PCT polyester plastic water cup. The dispersant used in this embodiment is BYK-161 dispersant; the antioxidant used is a complex of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1; the toughening agent used is maleic anhydride-grafted POE; and the lubricant used is a complex of zinc stearate and N,N'-ethylene bis-stearamide in a mass ratio of 1:1.5. In this embodiment, the temperatures of each section of the extruder are set as follows: Zone 1 250℃, Zone 2 255℃, Zone 3 260℃, Zone 4 265℃, Zone 5 275℃, and Die Head 280℃; the screw speed is controlled at 200 rpm.

[0029] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 does not add silane-modified graphene-loaded silver nanoparticles, but instead uses an equal amount of Tritan copolyester.

[0030] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that no modified zinc oxide / silver nanocomposite particles are added in Comparative Example 2; instead, an equal amount of Tritan copolyester is used.

[0031] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that in Comparative Example 3, an equal amount of nano-silver is used instead of silane-modified graphene-loaded silver nanoparticles and modified zinc oxide / silver nanocomposite particles.

[0032] Performance testing I. Antibacterial Properties: The plastic water cups obtained in Examples 1-5 and Comparative Examples 1-3 were cut into 10mm × 10mm samples and sterilized by ultraviolet irradiation for 3 hours. The Escherichia coli strain was activated and prepared into a bacterial suspension with a concentration of 3 × 10⁴ CFU / ml. The samples were placed in the bacterial suspension and shaken at 300 rpm for 5 minutes at room temperature. 1 mL of the bacterial suspension was diluted 100 times, and 1 mL of the diluted bacterial suspension was inoculated into agar medium and cultured at 37°C for 16 hours. Colony counting was performed according to the method in GB / T 15979, and the inhibition rate was calculated. The inhibition rate = (average number of colonies before sample shaking - average number of colonies after sample shaking) / average number of colonies before sample shaking × 100%. The results are shown in Table 1.

[0033] II. Impact strength: The impact strength of the plastic water cups obtained in Examples 1-5 and Comparative Examples 1-3 was tested according to the method in GB / T 1843, and the results are shown in Table 1.

[0034] The specific test results are as follows: Table 1 Performance Test Results

[0035] As can be seen from the test results in Table 1, the modified PCT polyester plastic water cup provided in this application has excellent antibacterial rate and high impact strength.

[0036] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A modified PCT polyester plastic water cup, characterized in that: The raw materials, by weight percentage, include 87.5-93% Tritan copolyester, 0.5-1.5% silane-modified graphene-supported silver nanoparticles, 1-2.5% modified zinc oxide / silver nanocomposite particles, 0.5-1% dispersant, 0.2-0.5% antioxidant, 3-6% toughening agent, and 0.5-1% lubricant.

2. The modified PCT polyester plastic water cup according to claim 1, characterized in that: The raw materials, by weight percentage, include 91% Tritan copolyester, 1% silane-modified graphene-supported silver nanoparticles, 1.5% modified zinc oxide / silver nanocomposite particles, 0.8% dispersant, 0.4% antioxidant, 4.5% toughening agent, and 0.8% lubricant.

3. A modified PCT polyester plastic water cup according to claim 1, characterized in that: The silane-modified graphene-supported silver nanoparticles are prepared from the following raw materials in parts by weight: 0.4-0.6 parts graphene oxide powder, 300-450 parts ethanol, 125-185 parts deionized water, 0.8-1.2 parts silane coupling agent KH570, and 0.2-0.3 parts silver nitrate.

4. A modified PCT polyester plastic water cup according to claim 3, characterized in that: The method for preparing silane-modified graphene-supported silver nanoparticles includes the following steps: S1. Add 0.4-0.6 parts of graphene oxide powder to a mixed solvent of 300-450 parts of ethanol and 100-150 parts of deionized water, and sonicate for 30-60 minutes to obtain a graphene oxide dispersion. S2. Add 0.8-1.2 parts of silane coupling agent KH570 to the graphene oxide dispersion, stir evenly, adjust the pH of the mixed solution to 8-9, and then stir at 60-70℃ for 12-16h to obtain the initial dispersion. S3. Dissolve 0.2-0.3 parts of silver nitrate in 25-35 parts of deionized water, adjust the pH of the solution to 9-10, and stir until completely dissolved to obtain a silver ion solution; add the silver ion solution to the initial dispersion, and stir at room temperature and a stirring speed of 600-700 rpm for 1-2 hours to allow the reaction to occur; after the reaction is complete, centrifuge the mixed dispersion for 10-15 minutes, remove the supernatant, wash the precipitate with distilled water, and centrifuge again. Repeat the operation several times, and freeze-dry the precipitate for 48-60 hours to obtain silane-modified graphene-supported silver nanoparticles.

5. A modified PCT polyester plastic water cup according to claim 1, characterized in that: The modified zinc oxide / silver nanocomposite particles are prepared from the following raw materials in parts by weight: 1-2 parts zinc oxide / silver nanocomposite particles, 60-120 parts anhydrous ethanol, and 2-4 parts phenyltriethoxysilane.

6. A modified PCT polyester plastic water cup according to claim 5, characterized in that: The zinc oxide / silver nanocomposite particles are prepared from the following raw materials in parts by weight: 0.1-0.15 parts anhydrous stannous chloride, 100-150 parts hydrochloric acid solution, 0.4-0.6 parts nano zinc oxide, 100-150 parts deionized water, 200-300 parts silver ammonia solution, and 0.5-0.8 parts formaldehyde in an ethanol aqueous solution.

7. A modified PCT polyester plastic water cup according to claim 6, characterized in that: The preparation method of the zinc oxide / silver nanocomposite particles includes the following steps: Dissolve 0.1-0.15 parts of anhydrous stannous chloride in 100-150 parts of hydrochloric acid solution; then add 0.4-0.6 parts of nano-zinc oxide, and stir continuously at room temperature for 30-50 min. Centrifuge to recover the precipitate, then wash several times with water. Disperse the precipitate in 100-150 parts of deionized water to obtain an activation solution of nano-zinc oxide-stannous ion complex; add 100-150 parts of silver ammonia solution to the activation solution, stir for 30-40 min, and filter to obtain nano-zinc oxide-silver active species; disperse the nano-zinc oxide-silver active species in 100-150 parts of silver ammonia solution and stir evenly, then add 0.5-0.8 parts of formaldehyde in ethanol aqueous solution; stir again for 30-40 min, then filter and rinse with ultrapure water; finally, vacuum dry at 50-60℃ for 24-30 h to obtain zinc oxide / silver nanocomposite particles.

8. A modified PCT polyester plastic water cup according to claim 5, characterized in that: The preparation method of the modified zinc oxide / silver nanocomposite particles includes the following steps: Add 1-2 parts of zinc oxide / silver nanocomposite particles to 60-120 parts of anhydrous ethanol, adjust the pH of the solution to 8-9, and ultrasonically disperse for 30-40 min; then add 2-4 parts of phenyltriethoxysilane, and ultrasonically disperse again for 30-40 min; finally, heat and stir the resulting mixture in an oil bath at 50-60℃ for 24-30 h; after the reaction is completed, centrifuge the obtained powder, wash it several times with anhydrous ethanol, and finally vacuum dry it at 50-60℃ for 24-30 h to obtain modified zinc oxide / silver nanocomposite particles.

9. A method for preparing a modified PCT polyester plastic water cup according to any one of claims 1-8, characterized in that: Includes the following steps: S1. Weigh the Tritan copolyester, silane-modified graphene-supported silver nanoparticles, modified zinc oxide / silver nanocomposite particles, dispersant, antioxidant, toughening agent, and lubricant by mass percentage; place the Tritan copolyester and toughening agent in a vacuum drying oven and dry at 100-110℃ for 4-6 hours; Add the above raw materials to a high-speed mixer and mix at 1000-1500 rpm for 10-15 minutes to obtain a premix. S2. Add the premixed material to the extruder for melt extrusion. After extrusion, cool and granulate to obtain masterbatch. Place the masterbatch in a vacuum drying oven and dry at 100-110℃ for 4-6 hours. Add the dried masterbatch to the injection molding machine to injection mold into water cup products. After the molded products are cooled and demolded, place them in an oven at 80-90℃ for 2-4 hours and then slowly cool to room temperature to obtain modified PCT polyester plastic water cups.

10. The method for preparing a modified PCT polyester plastic water cup according to claim 9, characterized in that: The temperatures of each section of the extruder are set as follows: Zone 1 240-250℃, Zone 2 245-255℃, Zone 3 250-260℃, Zone 4 255-265℃, Zone 5 265-275℃, and Die Head 270-280℃; the screw speed is controlled at 100-200 rpm.

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