Graphene synergistic antibacterial PVC material and preparation method thereof

Abstract

The application relates to the technical field of antibacterial materials, and discloses a graphene synergistic antibacterial PVC material and a preparation method thereof; hydroxyethyl acrylate, methyl methacrylate and a dienyl urea pyrimidine compound are subjected to in-situ graft polymerization reaction on the surface of hydroxyethyl acrylate functionalized graphene; meanwhile, the dienyl urea pyrimidine compound contains dienyl groups and can be crosslinked to form a polymer with a spatial crosslinking network structure, and a pyrimidine crosslinked polymer modified graphene is prepared.The application has the advantages that: through the improvement of the above process and components, the prepared PVC material improves the synergistic antibacterial capacity between the nano copper particles and the modified graphene under the action of the modified graphene, thereby improving the bactericidal, antibacterial and bacteriostatic capacity of the PVC material, improving the antibacterial capacity of the product prepared from the PVC material, reducing the breeding of bacteria and viruses on the PVC material and the product, improving the value of the PVC material and the product, and improving the health of the user.

Description

Technical Field

[0001] This invention relates to the field of antibacterial materials technology, specifically to a graphene-synergistic antibacterial PVC material and its preparation method. Background Technology

[0002] Although polyvinyl chloride (PVC) has advantages such as low cost, good solvent resistance, and high chemical corrosion resistance, it does not have bactericidal properties and its mechanical strength is not high, which is not conducive to its practical application in antibacterial materials and other fields.

[0003] Inorganic antibacterial agents such as copper, silver, titanium dioxide, and graphene are non-toxic, environmentally friendly, inexpensive, and readily available, playing an important role in antibacterial materials. Among them, copper nanoparticles are widely used bactericides due to their rapid bactericidal speed and broad-spectrum activity. However, copper nanoparticles have the drawback of easily agglomerating, hindering their effective release for antibacterial purposes. This problem is usually solved by loading copper nanoparticles onto the surface of an antibacterial agent carrier. Increasing the loading capacity of the carrier for copper nanoparticles remains a research challenge.

[0004] Graphene oxide possesses excellent optical, electrical, and mechanical properties, making it suitable for applications as a bactericide, catalyst carrier, and antistatic agent, showing promising potential in polymer materials. The surface of graphene oxide contains abundant oxygen-containing functional groups, allowing for surface grafting modification. This process endows graphene oxide with new functions, improves its compatibility with the matrix, and enhances the overall performance of the material. Furthermore, graphene oxide can synergistically interact with antibacterial agents such as copper and titanium dioxide, improving the bactericidal performance of the material. Therefore, surface grafting modification of graphene oxide is of significant importance. Summary of the Invention

[0005] This invention solves the following technical problems: it prepares a graphene-supported copper nanoparticle antibacterial agent, which solves the problems that copper nanoparticle antibacterial agents are prone to agglomeration and that polyvinyl chloride does not have antibacterial properties.

[0006] This invention provides the following technical solution: a preparation process for a graphene-synergistic antibacterial PVC material, comprising the following raw materials in parts by weight: 68-87 parts polyvinyl chloride resin, 0.5-5 parts graphene-supported nano-copper antibacterial agent, and 13-27 parts additives; the preparation process of the graphene-synergistic antibacterial PVC material includes the following steps:

[0007] S11, pyrimidine crosslinked polymer modified graphene, and ethanol aqueous solution were added to a flask and dispersed by ultrasonic vibration. Then copper sulfate was added and soaked for 12-24 hours. Sodium borohydride was added and the mixture was stirred at room temperature for 3-8 hours. After filtration, washing with water, and drying, graphene-supported copper nanoparticle antibacterial agent was obtained.

[0008] S12. Add polyvinyl chloride resin, graphene-supported nano-copper antibacterial agent, and additives to the mixer, mix at high speed, and then plasticize and extrude in the extruder to obtain graphene synergistic antibacterial PVC material.

[0009] Furthermore, the additives include 2-3 parts organotin stabilizer, 10-22 parts epoxidized soybean oil, 0.5-1.5 parts oleamide, and 0.1-0.3 parts stearic acid.

[0010] Furthermore, the volume fraction of the ethanol-water solution is 30-50%; the mass fraction of the pyrimidine crosslinked polymer-modified graphene in the ethanol-water solution is controlled to be 0.8-5%.

[0011] Furthermore, the proportions of the reactants in S11 are: pyrimidine crosslinked polymer modified graphene: copper sulfate: sodium borohydride = 1g:(0.2-1.5)g:(1.1-8)g.

[0012] Furthermore, the preparation process of pyrimidine crosslinked polymer modified graphene includes the following steps:

[0013] S21. Add hydroxyethyl acrylate functionalized graphene and ethanol solvent to a flask, disperse by ultrasonic vibration, then add hydroxyethyl acrylate, methyl methacrylate, and diene urea pyrimidine compound, purge nitrogen gas into the flask, heat to 70-80℃, add azobisisobutyronitrile dropwise, stir for 2-3 hours, cool, filter, wash with ethanol, and dry to obtain pyrimidine crosslinked polymer modified graphene.

[0014] Furthermore, the proportions of the reactants in S21 are as follows: hydroxyethyl acrylate functionalized graphene, hydroxyethyl acrylate, methyl methacrylate, diene urea pyrimidine compound, azobisisobutyronitrile = 1g:(2-10)g:(4-25)g:(3.5-20)g:(0.08-0.4)g.

[0015] Furthermore, the preparation process of diene urea pyrimidine compounds includes the following steps:

[0016] S31. Add 4,6-diaminopyrimidine, isopropenyl-α,α-dimethylbenzyl isocyanate, and reaction solvent to a flask, purge with nitrogen, heat to 70-100℃ and reflux for 4-8 h, concentrate, wash with n-hexane, recrystallize with ethyl acetate to obtain diene urea pyrimidine compound.

[0017]

[0018] Furthermore, the ratio of each reactant in S31 is 4,6-diaminopyrimidine:isopropenyl-α,α-dimethylbenzyl isocyanate = 1g:(4.2-6.5)g.

[0019] Furthermore, the reaction solvent is 1,4-dioxane, tetrahydrofuran, ethyl acetate, or acetonitrile.

[0020] The present invention has the following technical effects: The present invention performs an in-situ graft polymerization reaction of hydroxyethyl acrylate, methyl methacrylate and diene urea pyrimidine compound on the surface of hydroxyethyl acrylate functionalized graphene. At the same time, the diene urea pyrimidine compound contains diene groups, which can crosslink to form a polymer with a spatial crosslinked network structure, thus obtaining pyrimidine crosslinked polymer modified graphene.

[0021] The graphene-grafted crosslinked polymer contains hydrophilic hydroxyl groups, exhibiting excellent dispersibility in ethanol-water solutions. It also contains a ureido-pyrimidine structure, allowing for better polydentate coordination with copper ions. This enables the uniform adsorption and loading of copper ions onto the graphene surface. Further reduction allows the generated nano-copper particle antibacterial agent to be uniformly loaded onto the pyrimidine crosslinked polymer-modified graphene. Furthermore, the pyrimidine crosslinked polymer-modified graphene contains a spatial crosslinked network structure, resulting in a larger specific surface area, which is beneficial for increasing the loading capacity of the nano-copper particle antibacterial agent, improving the aggregation of the nano-copper particles, and enabling effective release of the nano-copper particles. This results in a better synergistic antibacterial effect with graphene, enhancing the bactericidal performance of polyvinyl chloride (PVC).

[0022] The graphene-grafted crosslinked polymer contains methyl methacrylate structural units. Its polymer molecular chains have excellent compatibility with polyvinyl chloride, which allows graphene to be better dispersed in the polyvinyl chloride matrix, resulting in excellent reinforcing effect and improving the tensile properties and Shore hardness of polyvinyl chloride.

[0023] Through the above-mentioned process and component improvements, the PVC material obtained is enhanced by the effect of modified graphene, which improves the synergistic antibacterial ability between the nano-copper particles and the modified graphene. This improves the bactericidal, antibacterial, and bacteriostatic abilities of the PVC material, as well as the antibacterial ability of the products made from it. It reduces the growth of bacteria and viruses on PVC materials and products, enhances the value of PVC materials and products, and also improves the health of users. Detailed Implementation

[0024] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0025] Preparation process of hydroxyethyl acrylate functionalized graphene: 0.2 g of graphene oxide and 50 mL of thionyl chloride were added to a flask and refluxed at 75 °C for 24 h. After filtration and washing with acetone, the product was added to toluene and dispersed by ultrasonic vibration. Hydroxyethyl acrylate and triethylamine were added under nitrogen atmosphere and reacted at room temperature for 36 h. After washing with ethanol and drying, hydroxyethyl acrylate functionalized graphene was obtained.

[0026] Example 1

[0027] 1.2 g of 4,6-diaminopyrimidine, 6.2 g of isopropenyl-α,α-dimethylbenzyl isocyanate, and 60 mL of ethyl acetate were added to a flask. Nitrogen gas was introduced, and the mixture was heated to 80 °C and refluxed for 8 h. The mixture was concentrated, washed with n-hexane, and recrystallized from ethyl acetate to obtain a dienylureapyrimidine compound with the following structural formula:

[0028]

[0029] 0.1 g of hydroxyethyl acrylate functionalized graphene and 20 mL of ethanol solvent were added to a flask and dispersed by ultrasonic vibration. Then, 0.2 g of hydroxyethyl acrylate, 0.4 g of methyl methacrylate, and 0.35 g of diene urea pyrimidine compound were added. Nitrogen gas was introduced into the flask, the temperature was raised to 75 °C, 8 mg of azobisisobutyronitrile was added dropwise, the mixture was stirred and reacted for 3 h, cooled, filtered, washed with ethanol, and dried to obtain pyrimidine crosslinked polymer modified graphene.

[0030] 0.2g of pyrimidine crosslinked polymer modified graphene and 30% ethanol aqueous solution were added to a flask, and the mass fraction of pyrimidine crosslinked polymer modified graphene in the solution was controlled to be 0.8%. The mixture was dispersed by ultrasonic vibration, and then 0.04g of copper sulfate was added and soaked for 24h. Then 0.22g of sodium borohydride was added and the mixture was stirred at room temperature for 3h. The mixture was filtered, washed with water and dried to obtain graphene-supported copper nanoparticle antibacterial agent.

[0031] Add 820g of polyvinyl chloride resin, 5g of graphene-supported nano-copper antibacterial agent, 25g of organotin stabilizer, 140g of epoxidized soybean oil, 8g of oleic acid amide, and 3 parts of stearic acid to a mixer. Mix at high speed at 100℃ for 5 minutes. Then, plasticize and extrude the mixture in an extruder. The extruder barrel temperatures in zones I-VI are 150℃, 160℃, 165℃, 175℃, 185℃, and 200℃, respectively. Discharge the material to obtain graphene-synergistic antibacterial PVC material.

[0032] Example 2

[0033] 1.2 g of 4,6-diaminopyrimidine, 5 g of isopropenyl-α,α-dimethylbenzyl isocyanate, and 40 mL of 1,4-dioxane solvent were added to a flask, nitrogen gas was introduced, the mixture was heated to 100 °C and refluxed for 4 h, concentrated, washed with n-hexane, and recrystallized from ethyl acetate to obtain the dienylureapyrimidine compound.

[0034] 0.1 g of hydroxyethyl acrylate functionalized graphene and 50 mL of ethanol solvent were added to a flask and dispersed by ultrasonic vibration. Then, 0.5 g of hydroxyethyl acrylate, 1.6 g of methyl methacrylate and 1 g of diene urea pyrimidine compound were added. Nitrogen gas was introduced into the flask and the temperature was raised to 70 °C. 22 mg of azobisisobutyronitrile was added dropwise and the mixture was stirred for 2 h. After cooling, the mixture was filtered, washed with ethanol, and dried to obtain pyrimidine crosslinked polymer modified graphene.

[0035] 0.2g of pyrimidine crosslinked polymer modified graphene and 50% ethanol aqueous solution were added to a flask, and the mass fraction of pyrimidine crosslinked polymer modified graphene in the solution was controlled to be 3%. The mixture was dispersed by ultrasonic vibration, and then 0.18g of copper sulfate was added and soaked for 12h. Then 0.9g of sodium borohydride was added and the mixture was stirred at room temperature for 5h. The mixture was filtered, washed with water and dried to obtain graphene-supported copper nanoparticle antibacterial agent.

[0036] Add 750g of polyvinyl chloride resin, 30g of graphene-supported nano-copper antibacterial agent, 20g of organotin stabilizer, 200g of epoxidized soybean oil, 15g of oleic acid amide, and 1 part of stearic acid to a mixer. Mix at high speed for 5 minutes at a mixing temperature of 80℃. Then, plasticize and extrude the mixture in an extruder. The extruder barrel temperatures in zones I-VI are 150℃, 160℃, 165℃, 175℃, 185℃, and 200℃, respectively. Discharge the material to obtain graphene-synergistic antibacterial PVC material.

[0037] Example 3

[0038] 1.2 g of 4,6-diaminopyrimidine, 7.8 g of isopropenyl-α,α-dimethylbenzyl isocyanate, and 80 mL of tetrahydrofuran solvent were added to a flask, nitrogen gas was introduced, the mixture was heated to 70 °C and refluxed for 4 h, concentrated, washed with n-hexane, and recrystallized from ethyl acetate to obtain the dienylureapyrimidine compound.

[0039] 0.1 g of hydroxyethyl acrylate functionalized graphene and 80 mL of ethanol solvent were added to a flask and dispersed by ultrasonic vibration. Then, 1 g of hydroxyethyl acrylate, 2.5 g of methyl methacrylate, and 2 g of diene urea pyrimidine compound were added. Nitrogen gas was introduced into the flask, the temperature was raised to 75 °C, 40 mg of azobisisobutyronitrile was added dropwise, the mixture was stirred and reacted for 2 h, cooled, filtered, washed with ethanol, and dried to obtain pyrimidine crosslinked polymer modified graphene.

[0040] 0.2g of pyrimidine crosslinked polymer modified graphene and 40% ethanol aqueous solution were added to a flask, and the mass fraction of pyrimidine crosslinked polymer modified graphene in the solution was controlled to be 5%. The mixture was dispersed by ultrasonic vibration, and then 0.3g of copper sulfate was added and soaked for 24h. Then 1.6g of sodium borohydride was added and the mixture was stirred at room temperature for 8h. The mixture was filtered, washed with water and dried to obtain graphene-supported copper nanoparticle antibacterial agent.

[0041] Add 720g of polyvinyl chloride resin, 50g of graphene-supported nano-copper antibacterial agent, 20g of organotin stabilizer, 150g of epoxidized soybean oil, 5g of oleic acid amide, and 3 parts of stearic acid to a mixer. Mix at high speed at 70℃ for 10 minutes. Then, plasticize and extrude the mixture in an extruder. The extruder barrel temperatures in zones I-VI are 150℃, 160℃, 165℃, 175℃, 185℃, and 200℃, respectively. Discharge the material to obtain graphene-synergistic antibacterial PVC material.

[0042] Comparative Example 1

[0043] 1.2 g of 4,6-diaminopyrimidine, 6.2 g of isopropenyl-α,α-dimethylbenzyl isocyanate, and 60 mL of ethyl acetate solvent were added to a flask, nitrogen gas was introduced, the mixture was heated to 90 °C and refluxed for 8 h, concentrated, washed with n-hexane, and recrystallized from ethyl acetate to obtain the dienylureapyrimidine compound.

[0044] 20 mL of ethanol solvent was added to a flask and dispersed by ultrasonic vibration. Then, 0.2 g of hydroxyethyl acrylate, 0.4 g of methyl methacrylate, and 0.35 g of diene urea pyrimidine compound were added. Nitrogen gas was introduced into the flask, the temperature was raised to 75 °C, 8 mg of azobisisobutyronitrile was added dropwise, the mixture was stirred and reacted for 3 h, cooled, filtered, washed with ethanol, and dried to obtain the pyrimidine crosslinked polymer.

[0045] 0.2g of pyrimidine crosslinked polymer and 30% ethanol aqueous solution were added to a flask, and the mass fraction of pyrimidine crosslinked polymer in the solution was controlled to be 0.8%. The mixture was dispersed by ultrasonic vibration, and then 0.04g of copper sulfate was added and soaked for 24h. Then 0.22g of sodium borohydride was added and the mixture was stirred at room temperature for 3h. The mixture was filtered, washed with water and dried to obtain polymer-loaded copper nanoparticle antibacterial agent.

[0046] Add 820g of polyvinyl chloride resin, 5g of polymer-loaded nano-copper antibacterial agent, 25g of organotin stabilizer, 140g of epoxidized soybean oil, 8g of oleic acid amide, and 3 parts of stearic acid to a mixer. Mix at high speed for 5 minutes at a mixing temperature of 100℃. Then, plasticize and extrude the mixture in an extruder. The extruder barrel temperatures in zones I-VI are 150℃, 160℃, 165℃, 175℃, 185℃, and 200℃, respectively. Discharge the material to obtain antibacterial polyvinyl chloride.

[0047] Comparative Example 2

[0048] 0.1 g of hydroxyethyl acrylate functionalized graphene and 20 mL of ethanol solvent were added to a flask and dispersed by ultrasonic vibration. Then, 0.2 g of hydroxyethyl acrylate and 0.4 g of methyl methacrylate were added, nitrogen gas was introduced into the flask, the temperature was raised to 75 °C, 8 mg of azobisisobutyronitrile was added dropwise, the mixture was stirred and reacted for 3 h, cooled, filtered, washed with ethanol, and dried to obtain polymer-modified graphene.

[0049] 0.2g of polymer-modified graphene and 30% ethanol aqueous solution were added to a flask, and the mass fraction of polymer-modified graphene in the solution was controlled to be 0.8%. The mixture was dispersed by ultrasonic vibration, and then 0.04g of copper sulfate was added and soaked for 24h. Then 0.22g of sodium borohydride was added and the mixture was stirred at room temperature for 3h. The mixture was filtered, washed with water, and dried to obtain graphene-supported copper nanoparticle antibacterial agent.

[0050] Add 820g of polyvinyl chloride resin, 5g of graphene-supported nano-copper antibacterial agent, 25g of organotin stabilizer, 140g of epoxidized soybean oil, 8g of oleic acid amide, and 3 parts of stearic acid to a mixer. Mix at high speed at 100℃ for 5 minutes. Then, plasticize and extrude the mixture in an extruder. The extruder barrel temperatures in zones I-VI are 150℃, 160℃, 165℃, 175℃, 185℃, and 200℃, respectively. Discharge the material to obtain graphene-synergistic antibacterial PVC material.

[0051] Comparative Example 3

[0052] 1.2 g of 4,6-diaminopyrimidine, 6.2 g of isopropenyl-α,α-dimethylbenzyl isocyanate, and 60 mL of ethyl acetate solvent were added to a flask, nitrogen gas was introduced, the mixture was heated to 90 °C and refluxed for 8 h, concentrated, washed with n-hexane, and recrystallized from ethyl acetate to obtain the dienylureapyrimidine compound.

[0053] 0.1 g of hydroxyethyl acrylate functionalized graphene and 20 mL of ethanol solvent were added to a flask and dispersed by ultrasonic vibration. Then, 0.2 g of hydroxyethyl acrylate, 0.4 g of methyl methacrylate, and 0.35 g of diene urea pyrimidine compound were added. Nitrogen gas was introduced into the flask, the temperature was raised to 75 °C, 8 mg of azobisisobutyronitrile was added dropwise, the mixture was stirred and reacted for 3 h, cooled, filtered, washed with ethanol, and dried to obtain pyrimidine crosslinked polymer modified graphene.

[0054] Add 820g of polyvinyl chloride resin, 5g of pyrimidine crosslinked polymer modified graphene, 25g of organotin stabilizer, 140g of epoxidized soybean oil, 8g of oleamide, and 3 parts of stearic acid to a mixer. Mix at high speed for 5 minutes at 100℃. Then, plasticize and extrude the mixture in an extruder. The extruder barrel temperatures in zones I-VI are 150℃, 160℃, 165℃, 175℃, 185℃, and 200℃, respectively. Discharge the material to obtain graphene-synergistic antibacterial PVC material.

[0055] Setting up experimental groups: The polyvinyl chloride samples prepared in each example and comparative example were cut into sheet-like experimental samples and added to PBS buffer solution containing E. coli culture (concentration 10). 6 The bacterial culture was prepared by shaking at 37°C (CFU / mL) on a shaker and adjusting the shaking contact time. 1 mL of the bacterial culture was transferred and serially diluted 10-fold. Then, 0.1 mL of each concentration gradient of the bacterial culture was transferred and coated onto an agar plate. Finally, the culture was incubated at 37°C for 24 h. The bacterial count was then determined.

[0056] Set up a blank control group: Prepare a PBS buffer solution (concentration 10) containing E. coli bacterial culture. 6 The bacterial culture was prepared by shaking at 37°C (CFU / mL) on a shaker and adjusting the shaking contact time. 1 mL of the bacterial culture was transferred and serially diluted 10-fold. Then, 0.1 mL of each concentration gradient of the bacterial culture was transferred and coated onto an agar plate. Finally, the culture was incubated at 37°C for 24 h. The bacterial count was then determined.

[0057] Calculate the sterilization rate Q. A represents the bacterial count in the blank group, and B represents the bacterial count in the experimental group.

[0058] Table 1. Test table for sterilization rate of polyvinyl chloride.

[0059]

[0060] After antibacterial performance testing, the graphene-modified antibacterial PVC materials prepared in each embodiment achieved a bactericidal rate of 99.2-99.9% against Escherichia coli after 12 hours of shaking contact. The pyrimidine crosslinked polymer-modified graphene contains ureido-pyrimidine groups, which undergo polydentate coordination with copper ions, achieving uniform adsorption and loading of copper ions. Further reduction allows the generated nano-copper particle antibacterial agent to be uniformly loaded into the pyrimidine crosslinked polymer-modified graphene. Furthermore, the pyrimidine crosslinked polymer-modified graphene contains a spatial crosslinked network structure with a larger specific surface area, which is beneficial for increasing the loading capacity of the nano-copper particle antibacterial agent, improving the aggregation of the nano-copper particles, and enabling effective release of the nano-copper particles. This results in a better synergistic antibacterial effect with graphene, significantly improving the bactericidal rate of PVC.

[0061] The difference between Comparative Example 1 and Example 1 is that only a pyrimidine crosslinked polymer without graphene was prepared as a carrier for the antibacterial agent of copper nanoparticles. Although the antibacterial rate reached 96.6%, the antibacterial rate was slightly lower than that of Example 1.

[0062] The difference between Comparative Example 2 and Example 1 is that no diene ureidopyrimidine compound was added when preparing the polymer-modified graphene. The polymer-modified graphene does not contain ureido-pyrimidine groups and spatial cross-linked network structure, resulting in poor adsorption performance for copper ions and low loading of antibacterial agent in nano-copper particles. Therefore, the antibacterial rate of polyvinyl chloride is not good.

[0063] The difference between Comparative Example 3 and Example 1 is that the pyrimidine crosslinked polymer modified graphene does not have nano-copper particles loaded, and the polyvinyl chloride has the lowest bactericidal rate and the worst antibacterial rate.

[0064] The polyvinyl chloride prepared in each embodiment and comparative example was injection molded into standard specimens, and its mechanical properties were tested using a universal testing machine and a Shore hardness tester.

[0065] Table 2 Test Table of Mechanical Properties of Polyvinyl Chloride

[0066] Tensile strength (MPa) Elongation at break (%) Shore A hardness Example 1 32.4 306.5 83 Example 2 41.1 265.4 90 Example 3 34.7 282.3 88 Comparative Example 1 26.4 252.0 77 Comparative Example 2 32.9 300.2 84 Comparative Example 3 32.2 309.1 83

[0067] The graphene oxide prepared in the examples, after copolymer grafting modification, has crosslinked polymers containing methyl methacrylate structural units. The polymer molecular chains have good compatibility with polyvinyl chloride, which can improve the compatibility between graphene and polyvinyl chloride, and improve the tensile properties and Shore A hardness of polyvinyl chloride.

[0068] Comparative Example 1, which does not contain graphene oxide, exhibits the worst mechanical properties in polyvinyl chloride.

[0069] The graphene oxides in Comparative Examples 2 and 3 were also modified by copolymer grafting, resulting in better mechanical properties of polyvinyl chloride.

[0070] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A preparation process for a graphene-synergistic antibacterial PVC material, characterized in that, The graphene-coated antibacterial PVC material comprises the following raw materials in parts by weight: 68-87 parts polyvinyl chloride resin, 0.5-5 parts graphene-supported nano-copper antibacterial agent, and 13-27 parts additives. The preparation process of the graphene-synergistic antibacterial PVC material includes the following steps: S11, pyrimidine crosslinked polymer modified graphene, and ethanol aqueous solution were added to a flask and dispersed by ultrasonic vibration. Then copper sulfate was added and soaked for 12-24 hours. Sodium borohydride was added and the mixture was stirred at room temperature for 3-8 hours. After filtration, washing with water, and drying, graphene-supported copper nanoparticle antibacterial agent was obtained. S12. Add polyvinyl chloride resin, graphene-supported nano-copper antibacterial agent, and additives to the mixer, mix at high speed, and then plasticize and extrude in the extruder to obtain graphene synergistic antibacterial PVC material. The ratio of each reactant in S11 is: pyrimidine crosslinked polymer modified graphene: copper sulfate: sodium borohydride = 1g:(0.2-1.5)g:(1.1-8)g; The preparation process of the pyrimidine crosslinked polymer modified graphene includes the following steps: S21. Add hydroxyethyl acrylate functionalized graphene and ethanol solvent to a flask, disperse by ultrasonic vibration, then add hydroxyethyl acrylate, methyl methacrylate, and diene urea pyrimidine compound, purge nitrogen gas into the flask, heat to 70-80℃, add azobisisobutyronitrile dropwise, stir the reaction for 2-3 hours, cool, filter, wash with ethanol, and dry to obtain pyrimidine crosslinked polymer modified graphene; The proportions of the reactants in S21 are as follows: hydroxyethyl acrylate functionalized graphene, hydroxyethyl acrylate, methyl methacrylate, diene urea pyrimidine compound, azobisisobutyronitrile = 1g:(2-10)g:(4-25)g:(3.5-20)g:(0.08-0.4)g; The preparation process of the diene urea pyrimidine compound includes the following steps: S31. Add 4,6-diaminopyrimidine, isopropenyl-α,α-dimethylbenzyl isocyanate, and reaction solvent to a flask, purge with nitrogen, heat to 90-100℃ and reflux for 4-8 h, concentrate, wash with n-hexane, recrystallize with ethyl acetate to obtain diene ureidopyrimidine compound.

2. The preparation process of the graphene-synergistic antibacterial PVC material according to claim 1, characterized in that, The additives include 2-3 parts organotin stabilizer, 10-22 parts epoxidized soybean oil, 0.5-1.5 parts oleamide, and 0.1-0.3 parts stearic acid.

3. The preparation process of the graphene-synergistic antibacterial PVC material according to claim 1, characterized in that, The volume fraction of the ethanol-water solution is 30-50%; the mass fraction of the pyrimidine crosslinked polymer-modified graphene in the ethanol-water solution is controlled to be 0.8-5%.

4. The preparation process of the graphene-synergistic antibacterial PVC material according to claim 1, characterized in that, The ratio of reactants in S31 is 4,6-diaminopyrimidine:isopropenyl-α,α-dimethylbenzyl isocyanate = 1g:(4.2-6.5)g.

5. The preparation process of the graphene-synergistic antibacterial PVC material according to claim 1, characterized in that, The reaction solvent is 1,4-dioxane, tetrahydrofuran, ethyl acetate, or acetonitrile.

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