A composite antibacterial and antiviral material, its preparation method and application

Abstract

The present invention discloses a composite antibacterial and antiviral material, a preparation method thereof and an application thereof. The composite antibacterial and antiviral material includes polyaniline graphene, graphene oxide and nano metal; wherein the polyaniline graphene and the graphene oxide are arranged alternately and parallelly, and the nano metal is uniformly and neatly distributed between the layers of the polyaniline graphene and the graphene oxide, so that the composite antibacterial and antiviral material has a "maze structure", and the nano metal includes nano copper and / or nano silver. The composite antibacterial and antiviral material in the present invention has good stability and excellent antibacterial and antiviral effects; at the same time, the preparation process of the composite antibacterial and antiviral material in the present invention is simple, low in cost, and environmentally friendly.

Description

Technical Field

[0001] The present invention belongs to the technical field of graphene composites, and relates to a composite antibacterial and antiviral material, its preparation method and application, and particularly relates to a polyaniline graphene / graphene oxide / nano-metal composite antibacterial and antiviral material, its preparation method and application. Background Art

[0002] With the development of the times and the continuous improvement of living standards, people's awareness of health and environmental protection has been continuously enhanced. As the main material for inhibiting the growth of harmful bacteria, antibacterial materials have been widely used in various fields. Traditional antibacterial agents are mainly divided into two categories: inorganic antibacterial agents and organic antibacterial agents. Among them, inorganic antibacterial agents mainly use antibacterial metal materials such as Ag, Ti, Cu, etc. loaded on a certain carrier to become antibacterial materials through ion exchange, adsorption and chemical combination. However, antibacterial metal materials are generally expensive and have a high cost. Organic antibacterial materials are mainly synthesized from organic molecules, with rich varieties and low costs. However, organic molecules are easily decomposed and unstable under high-temperature conditions, so the stability of organic antibacterial materials is poor. Graphene, as a two-dimensional material with a super-large specific surface area and having certain antibacterial properties, is an ideal carrier. However, due to the hydrophobic characteristics of graphene, its dispersibility in aqueous solution is poor. Therefore, it is an urgent problem to provide an antibacterial and antiviral material with low price and excellent performance. Summary of the Invention

[0003] The main purpose of the present invention is to provide a composite antibacterial and antiviral material, its preparation method and application, so as to overcome the deficiencies of the prior art.

[0004] To achieve the foregoing invention purpose, the technical solutions adopted by the present invention include:

[0005] An embodiment of the present invention provides a composite antibacterial and antiviral material, which includes: polyaniline graphene, graphene oxide and nano-metal; wherein the polyaniline graphene and the graphene oxide are arranged alternately and parallelly, and the nano-metal is uniformly and neatly distributed between the layers of the polyaniline graphene and the graphene oxide, so that the composite antibacterial and antiviral material has a "maze structure", and the nano-metal includes nano-copper and / or nano-silver.

[0006] An embodiment of the present invention also provides a preparation method of a composite antibacterial and antiviral material, which includes:

[0007] Providing a dispersion liquid containing polyaniline graphene, graphene oxide, copper sulfate and / or silver nitrate as an electrolyte;

[0008] And, making the electrolyte, the cathode and the anode jointly construct an electrochemical reaction system, and using an electrodeposition technique to deposit a polyaniline graphene / graphene oxide / nano-metal material on the surface of the cathode, so as to obtain a composite antibacterial and antiviral material.

[0009] The embodiment of the present invention also provides a composite antibacterial and antiviral material prepared by the foregoing preparation method.

[0010] The embodiment of the present invention also provides an antibacterial and antiviral product, which at least includes the foregoing composite antibacterial and antiviral material.

[0011] The embodiment of the present invention also provides a coating composition, including a base coating, which further includes the foregoing composite antibacterial and antiviral material.

[0012] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0013] (1) The composite antibacterial and antiviral material (i.e., polyaniline graphene / graphene oxide / nano metal material) in the present invention is an aqueous antibacterial material, and the entire production process and the final use of the antibacterial material are non-toxic and environmentally friendly.

[0014] (2) Compared with the traditional inorganic antibacterial agent materials mainly composed of antibacterial metals and being expensive, the composite antibacterial and antiviral material in the present invention is mainly composed of polyaniline graphene and graphene oxide materials, and the content of silver or copper ions in the material is only 1% - 30%, greatly reducing the material cost.

[0015] (3) Compared with the disordered arrangement of the graphene oxide antibacterial material prepared by the traditional redox method, the electrodeposition process in the present invention can orient the distribution of graphene and graphene oxide to form a flat shielding layer, which can not only improve the antibacterial and antiviral effects of the coating, but also improve the water resistance, acid and alkali resistance and other properties of the coating.

[0016] (4) Compared with the traditional antibacterial agents, the composite antibacterial and antiviral material in the present invention is stable at high temperatures and will not be decomposed, and has good antibacterial and antiviral effects; through detection, according to GB / T21866 - 2008 and T / CNCIA 03002 - 2020, when only 0.2% of the formulation components of the polyaniline graphene / graphene oxide / nano metal antibacterial material is added as an antibacterial agent in the coating, the antibacterial and antiviral effects on Escherichia coli and Staphylococcus aureus can both reach more than 99.99%. The antiviral rate of influenza A virus H3N2 is more than 99.90%, and the antiviral rate of enterovirus 71 is more than 95.00%. Description of the Drawings

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0018] Figures 1 - 2 It is the SEM image of the polyaniline graphene / graphene oxide / nano - copper composite antibacterial and antiviral material prepared in Example 1 of the present invention. Detailed implementation manners

[0019] In view of the defects of the prior art, through long - term research and a large number of practices by the inventors of this case, the technical solution of the present invention has been proposed. The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0020] Specifically, as an aspect of the technical solution of the present invention, a composite antibacterial and antiviral material it relates to includes: polyaniline graphene, graphene oxide and nano - metal; wherein the polyaniline graphene and the graphene oxide are arranged alternately and parallelly, and the nano - metal is evenly and neatly distributed between the layers of the polyaniline graphene and the graphene oxide, so that the composite antibacterial and antiviral material has a "labyrinth structure", and the nano - metal includes nano - copper and / or nano - silver.

[0021] In some preferred embodiments, the nano - metal is a mixture of nano - copper and nano - silver.

[0022] In some preferred embodiments, when the composite antibacterial and antiviral material contains both nano - copper and nano - silver, it shows the most excellent antibacterial and antiviral effects.

[0023] In some preferred embodiments, the composite antibacterial and antiviral material includes the following components by mass percentage: 35 - 50% polyaniline graphene, 35 - 50% graphene oxide, 1 - 30% nano - metal.

[0024] In some preferred embodiments, the diameter of the polyaniline - modified graphene is 0.1 - 50 μm, and the number of layers is 1 - 50 layers.

[0025] In some preferred embodiments, the diameter of the graphene oxide is 0.1 - 50 μm, and the number of layers is 1 - 50 layers.

[0026] In some preferred embodiments, the particle size of the nano - metal is 3 - 500 nm.

[0027] In some preferred embodiments, the antiviral rate of the composite antibacterial and antiviral material against the influenza A virus H3N2 is above 99.90%.

[0028] In some preferred embodiments, the antiviral rate of the composite antibacterial and antiviral material against enterovirus 71 is above 95.00%.

[0029] In some preferred embodiments, the antibacterial rate of the composite antibacterial and antiviral material against Escherichia coli is above 99.99%.

[0030] In some preferred embodiments, the antibacterial rate of the composite antibacterial and antiviral material against Staphylococcus aureus is above 99.99%.

[0031] Another aspect of the embodiments of the present invention also provides a preparation method of the aforementioned composite antibacterial and antiviral material, which includes:

[0032] Providing a dispersion liquid containing polyaniline graphene, graphene oxide, copper sulfate, and / or silver nitrate as an electrolyte;

[0033] And, constructing an electrochemical reaction system with the electrolyte, a cathode, and an anode, and depositing polyaniline graphene / graphene oxide / nano metal material on the surface of the cathode by electroplating technology to obtain the composite antibacterial and antiviral material.

[0034] In some preferred embodiments, the preparation method of the composite antibacterial and antiviral material includes:

[0035] Mixing copper sulfate and / or silver nitrate, potassium nitrate, and water uniformly, and adjusting the pH value of the obtained solution to 8-10 to obtain a complex solution;

[0036] And, mixing the graphene oxide dispersion liquid, polyaniline graphene, and the complex solution uniformly to obtain the electrolyte.

[0037] Further, the mass ratio of the copper sulfate and / or silver nitrate to potassium nitrate is 1:1-4.

[0038] Further, the mass ratio of the copper sulfate and / or silver nitrate to graphene oxide in the electrolyte is 1:1-10.

[0039] Further, the mass ratio of polyaniline graphene to graphene oxide in the electrolyte is 1-2:1-2.

[0040] In some preferred embodiments, the time for depositing polyaniline graphene / graphene oxide / nano metal material on the surface of the cathode by the electroplating technology is 0.5-2 h.

[0041] In some preferred embodiments, the cathode and the anode are independently selected from a copper electrode or a silver electrode.

[0042] Further, when the polyaniline graphene / graphene oxide / nano metal material is a polyaniline graphene / graphene oxide / nano copper material, a copper electrode is used; when the polyaniline graphene / graphene oxide / nano metal material is a polyaniline graphene / graphene oxide / nano silver material, a silver electrode is used.

[0043] In some preferred embodiments, the method for preparing the composite antibacterial and antiviral material further includes: placing the polyaniline graphene / graphene oxide / nano copper material in ammonia water, stirring and reacting with ethylenediamine at 30-90 °C, and then performing washing and drying treatments to obtain the composite antibacterial and antiviral material.

[0044] Among them, ethylenediamine can adsorb free copper ions, and can improve the attachment efficiency of copper ions on graphene and graphene oxide.

[0045] Further, the mass ratio of ethylenediamine to graphene oxide is 1:1-4.

[0046] Further, the drying treatment method includes freeze-drying, the temperature of the freeze-drying is -30 to -20 °C, and the time is 12 to 48 h.

[0047] Further, the stirring reaction time is 1-4 h.

[0048] In some preferred embodiments, the method for preparing the composite antibacterial and antiviral material further includes: reacting a mixed reaction system containing graphene, aniline and an initiator at 0-10 °C to obtain polyaniline graphene.

[0049] Further, the mass ratio of graphene, aniline and the initiator is 1-5:10-20:20.

[0050] Further, the initiator includes ammonium persulfate, and is not limited thereto.

[0051] In some more specific embodiments, the method for preparing the composite antibacterial and antiviral material includes:

[0052] The graphene used in the present invention is graphene prepared by the detonation method, which has a unique "lotus-like" structure and can pierce bacteria more effectively. Moreover, due to the participation of metallic magnesium in the detonation method, a small amount of magnesium ions are attached to the surface of graphene, which can enhance the antibacterial effect.

[0053] In some more specific embodiments, the method for preparing the composite antibacterial and antiviral material includes:

[0054] (1) Stir graphene and polyvinylpyrrolidone evenly in water, and disperse them by ultrasonic wave to obtain a uniformly dispersed graphene suspension;

[0055] (2) Adjust the pH value of the graphene suspension with concentrated phosphoric acid, and then add aniline;

[0056] (3) Dissolve ammonium persulfate in concentrated phosphoric acid, stir evenly, and slowly titrate it into the graphene suspension under ice bath conditions for reaction;

[0057] (4) After the reaction, wash the pH value to neutral by centrifugation to obtain an aqueous polyaniline graphene slurry;

[0058] (5) Disperse graphite oxide in an aqueous solution, and disperse it by ultrasonic wave to obtain a stable graphene oxide suspension;

[0059] (6) Dissolve anhydrous copper sulfate in water, add potassium nitrate, stir at high speed until evenly dispersed, then adjust the pH value of the solution with sodium hydroxide to prepare a complexing solution, and then mix and stir evenly with the graphene oxide suspension and the polyaniline graphene slurry to obtain an electrolyte;

[0060] (7) Use copper plates as electrodes at both ends, and electroplate through an electrolytic cell for 0.5 - 2 h;

[0061] (8) Scrape off the polyaniline graphene / graphene oxide / nano - copper material deposited on the cathode copper plate, add ammonia water to adjust the pH to neutral, and then add ethylenediamine and stir and react at 30 - 90 °C for 1 - 4 h;

[0062] (9) Centrifuge and wash the reaction solution repeatedly until neutral, and then obtain the polyaniline graphene / graphene oxide / nano - copper material by freeze - drying, that is, the composite antibacterial and antiviral material.

[0063] Further, in step (1), the concentration of the graphene suspension is 0.1 g / L - 15 g / L, the mass ratio of graphene to polyvinylpyrrolidone is 1:0.1 - 2, the ultrasonic time is 0.2 - 8 h, and the ultrasonic power is 240 - 960 KW.

[0064] Further, in step (2), the pH value is 1 - 4, and the mass ratio of aniline to graphene is 1 - 10:1.

[0065] Further, in step (3), the mass ratio of ammonium persulfate to aniline is 2 - 4:1.

[0066] Further, in step (5), the concentration of the graphene oxide suspension is 0.1 g / L - 15 g / L, the ultrasonic time is 0.2 - 8 h, and the ultrasonic power is 240 - 960 KW.

[0067] Further, the mass ratio of the amount of copper sulfate anhydrous added in step (6) to potassium nitrate is 1:1 to 4; the mass ratio of copper sulfate anhydrous to graphene oxide is 1:1 to 10, and the mass of the polyaniline graphene solution to the graphene oxide solution is 1:1.

[0068] Further, in step (7), a copper plate is used as the electrode, and the electroplating time is 0.1 to 2 h.

[0069] Further, in step (8), the mass ratio of ethylenediamine added to graphene oxide is 1:1 to 4, the reaction temperature is 30 to 90 °C, and the reaction time is 0.1 to 4 h.

[0070] Further, the temperature of freeze-drying in step (9) is -30 to -20 °C, and the freeze-drying time is 12 to 48 h.

[0071] In the present invention, polyaniline graphene and graphene oxide are used as the main carriers of the inorganic-organic doped antibacterial material. Compared with the graphene oxide antibacterial material prepared by the redox method mostly used in the traditional technology, the present invention suddenly adopts the electrodeposition method, which can enable the polyaniline graphene and graphene oxide to be arranged directionally during the preparation process, forming a unique parallel structure. When water is used as the medium, the hydroxyl groups of graphene oxide carry negative charges and are evenly dispersed in water. As a highly conductive material, graphene can improve the deposition efficiency of graphene oxide and copper ions during the electrodeposition process. However, the water solubility of graphene itself is not good. Through the modification of polyaniline, the graphene is negatively charged to improve its dispersibility in water. Under the action of electrodeposition, the charge migrates, and the polyaniline graphene and graphene oxide sheets can be deposited on the imprinting plate directionally and evenly, while silver or copper ions are neatly arranged between the sheets of polyaniline graphene and graphene oxide to form a "labyrinth structure". It not only utilizes the good shielding effect of its "labyrinth effect" to prevent the coating from being penetrated by bacteria and viruses, but also because of its large specific surface area and good structural stability and other characteristics, it can improve the stability of the antibacterial material and facilitate the attachment of silver or copper ions on the polyaniline graphene and graphene oxide. At the same time, the present invention utilizes graphene to catalyze the oxidative stress reaction of viruses, resulting in the death of viruses. The sharp sheet structures of graphene and graphene oxide can directly pierce the cell membrane to kill bacteria; through charge transfer, stimulate free radical reactions, and destroy the bacterial structure; it forms a synergistic effect with the adsorption and killing ability of nano-copper or nano-silver to microorganisms.

[0072] Another aspect of the embodiment of the present invention also provides an antibacterial and antiviral product, which at least includes the aforementioned composite antibacterial and antiviral material.

[0073] Another aspect of the embodiment of the present invention also provides a coating composition, including a base coating, which also includes the aforementioned composite antibacterial and antiviral material.

[0074] Furthermore, the base coating includes any one or a combination of two or more of waterborne polyurethane, waterborne acrylic, waterborne alkyd, waterborne fluorocarbon, waterborne epoxy, waterborne silicone, and waterborne inorganic coatings, and is not limited thereto.

[0075] Furthermore, the content of the composite antibacterial and antiviral material in the coating composition is 0.1 to 2 wt%, preferably 0.1 to 0.2 wt%.

[0076] The technical solutions of the present invention will be further described in detail below in conjunction with several preferred embodiments. These embodiments are implemented on the premise of the technical solutions of the invention, and detailed implementation manners and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0077] The experimental materials used in the following embodiments can be purchased from conventional biochemical reagent companies without special instructions. For example, the graphene used below is purchased from XHG020001 of Quanzhou Xinhe Graphene Research Institute Co., Ltd., and the graphene oxide is purchased from GP109 of Quanzhou Xinhe Graphene Research Institute Co., Ltd.

[0078] Example 1

[0079] A preparation method of a polyaniline graphene / graphene oxide / nano copper composite antibacterial and antiviral material includes the following steps:

[0080] (1) Graphene is ultrasonicated in an aqueous solution at a concentration of 0.1 g / L with 0.01 g / L of polyvinylpyrrolidone at a power of 240 KW for 0.5 h to obtain 500 mL of a uniformly dispersed graphene solution. Then, the pH value is adjusted to 4 with concentrated phosphoric acid, and after adding 0.5 g of aniline, the graphene solution is placed in an ice bath.

[0081] (2) 1 g of ammonium persulfate is dissolved in phosphoric acid, and is slowly added dropwise to the graphene solution containing aniline obtained in step (1) in an ice bath and reacted at 10 °C for 6 h. Then, the pH is washed to neutral by centrifugal washing repeatedly to obtain a polyaniline-modified graphene solution.

[0082] (3) Graphite oxide is ultrasonicated in an aqueous solution at a concentration of 0.1 g / L at a power of 240 KW for 0.5 h to obtain 500 mL of a uniformly dispersed graphene oxide solution.

[0083] (4) 500 mL of an aqueous solution of anhydrous copper sulfate is prepared at a concentration of 0.1 g / L. After the anhydrous copper sulfate solution is stirred evenly, 0.2 g of potassium nitrate is added and stirred continuously to prepare a complex solution, and the pH value is adjusted to neutral with NaOH. Then, the graphene oxide solution, the polyaniline graphene solution, and the complex solution are stirred evenly to prepare an electrolyte, wherein the mass ratio of polyaniline graphene to graphene oxide is 1:2.

[0084] (5) Place copper plates as the anode and cathode in the electrolyte solution, connect the power supply, and electroplate for 2 h. Scrape off the deposit on the cathode plate, add ammonia water to adjust the pH to neutral, then add 0.2 g of ethylenediamine and react at 90 °C for 0.1 h. Then repeatedly wash by centrifugation with water until the pH is about 8. Then freeze-dry at -30 °C for 12 h to obtain the polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material.

[0085] By detecting, in the components of the polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material, copper accounts for about 30 parts (parts by mass, the same below), graphene oxide accounts for about 35 parts, and polyaniline graphene accounts for about 35 parts. When this composite antibacterial and antiviral material is added to the water-based latex paint according to 0.1% of the components, the antibacterial rate can reach 99.99%, the antiviral rate against H3N2 virus can reach 99.97%, and the antiviral rate against enterovirus 71 can reach 95.89%. The SEM diagram of the polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material prepared in this example is as Figure 1 、 Figure 2 shown.

[0086] Example 2

[0087] A preparation method of a polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material includes the following steps:

[0088] (1) Mix graphene with polyvinylpyrrolidone at a concentration of 15 g / L in an aqueous solution with a power of 960 KW and ultrasonicate for 8 h to obtain 500 mL of a uniformly dispersed graphene solution. Then adjust the pH value to 2 with concentrated phosphoric acid. Then add 7.5 g of aniline and place the graphene solution in an ice bath.

[0089] (2) Dissolve 30 g of ammonium persulfate in phosphoric acid, slowly drop it into the graphene solution containing aniline obtained in step (1) in an ice bath, and react at 0 °C for 12 h. Then repeatedly wash by centrifugation to wash the pH to neutral to obtain a polyaniline-modified graphene solution.

[0090] (3) Ultrasonicate graphite oxide in an aqueous solution at a concentration of 15 g / L with a power of 960 KW for 8 h to obtain 500 mL of a uniformly dispersed graphene oxide solution.

[0091] (4) Prepare 500 mL of an aqueous solution of anhydrous copper sulfate at a concentration of 1.5 g / L. After stirring the anhydrous copper sulfate solution evenly, add 0.75 g of potassium nitrate and continue stirring to prepare a complexing solution and adjust the pH value to neutral with NaOH. Then stir the graphene oxide solution, the polyaniline graphene solution and the complexing solution evenly to prepare an electrolyte solution; among them, the mass ratio of polyaniline graphene to graphene oxide is 1:1.

[0092] (5) Place copper plates as the anode and cathode in the electrolyte solution, connect the power supply, and electroplate for 0.1 h. Scrape off the deposits on the cathode plate, add ammonia water to adjust the pH to neutral, then add 7.5 g of ethylenediamine and react at 30 °C for 4 h. Then repeatedly wash by centrifugation with clear water until the pH is about 8. Then freeze-dry at -20 °C for 48 h to obtain the polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material.

[0093] By detecting the components of the polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material, copper accounts for about 1 part, graphene oxide accounts for about 50 parts, and polyaniline graphene accounts for about 50 parts. When the composite antibacterial and antiviral material is added to the waterborne polyurethane topcoat at a component ratio of 0.2%, the antibacterial rate can reach 99.99%, the antiviral rate against H3N2 virus can reach 99.99%, and the antiviral rate against enterovirus 71 can reach 95.59%.

[0094] Example 3

[0095] A preparation method of a polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material, comprising the following steps:

[0096] (1) Disperse graphene in an aqueous solution at a concentration of 8 g / L in combination with 8 g / L of polyvinylpyrrolidone, and ultrasonicate at a power of 480 KW for 4 h to obtain 500 mL of a uniformly dispersed graphene solution. Then adjust the pH value to 3 with concentrated phosphoric acid. Then add 8 g of aniline and place the graphene solution in an ice bath.

[0097] (2) Dissolve 20 g of ammonium persulfate in phosphoric acid, and slowly drop it into the graphene solution containing aniline obtained in step (1) in an ice bath and react at 5 °C for 8 h. Then repeatedly wash by centrifugation to wash the pH to neutral to obtain a polyaniline-modified graphene solution.

[0098] (3) Disperse graphite oxide in an aqueous solution at a concentration of 8 g / L, and ultrasonicate at a power of 480 KW for 4 h to obtain 500 mL of a uniformly dispersed graphene oxide solution.

[0099] (4) Prepare 500 mL of an aqueous solution of anhydrous copper sulfate at a concentration of 2 g / L. After stirring the anhydrous copper sulfate solution evenly, add 2 g of potassium nitrate and continue to stir to prepare a complex solution, and adjust the pH value to neutral with NaOH. Then stir the graphene oxide solution, the polyaniline graphene solution and the complex solution evenly to prepare an electrolyte solution; among them, the mass ratio of polyaniline graphene to graphene oxide is 2:1.

[0100] (5) Place copper plates as the anode and cathode in the electrolyte, connect the power supply, and electroplate for 1 h. Scrape off the deposits on the cathode plate, add ammonia water to adjust the pH to neutral, then add 3 g of ethylenediamine and react at 80 °C for 4 h. Then repeatedly wash by centrifugation with clear water until the pH is about 8. Then freeze-dry at -30 °C for 24 h to obtain the polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material.

[0101] By detecting, in the components of the polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material, copper accounts for about 10 parts, graphene oxide accounts for about 45 parts, and polyaniline graphene accounts for about 45 parts. When this composite antibacterial and antiviral material is added to the waterborne alkyd topcoat at a component ratio of 0.2%, an antibacterial rate of 99.99%, an antiviral rate against H3N2 virus of 99.99%, and an antiviral rate against enterovirus 71 of 95.67% can be achieved.

[0102] Example 4

[0103] A preparation method of a polyaniline graphene / graphene oxide / nano-silver composite antibacterial and antiviral material, comprising the following steps:

[0104] (6) Mix graphene with polyvinylpyrrolidone at a concentration of 8 g / L in an aqueous solution, and ultrasonicate at a power of 480 KW for 4 h to obtain 500 mL of a uniformly dispersed graphene solution. Then adjust the pH value to 3 with concentrated phosphoric acid. Then add 8 g of aniline and place the graphene solution in an ice bath.

[0105] (7) Dissolve 20 g of ammonium persulfate in phosphoric acid, slowly drop it into the graphene solution containing aniline obtained in step (1) in an ice bath, and react at 5 °C for 8 h. Then repeatedly wash by centrifugation until the pH is washed to neutral to obtain a polyaniline-modified graphene solution.

[0106] (8) Ultrasonicate graphite oxide in an aqueous solution at a concentration of 8 g / L at a power of 480 KW for 4 h to obtain 500 mL of a uniformly dispersed graphene oxide solution.

[0107] (9) Prepare a 500 mL aqueous silver nitrate solution at a concentration of 2 g / L. After stirring the silver nitrate solution evenly, add 2 g of potassium nitrate and continue to stir to prepare a complex solution, and adjust the pH value to neutral with NaOH. Then stir the graphene oxide solution, the polyaniline graphene solution and the complex solution evenly to prepare an electrolyte; wherein, the mass ratio of polyaniline graphene to graphene oxide is 2:1.

[0108] (10) Place a silver plate as the anode and cathode in the electrolyte, connect the power supply, and electroplate for 1 h. Scrape off the deposit on the cathode plate, add ammonia water to adjust the pH to neutral, then add 3 g of ethylenediamine and react at 80 °C for 4 h. Then repeatedly wash by centrifugation with clear water until the pH is about 8. Then freeze-dry at -30 °C for 24 h to obtain the polyaniline graphene / graphene oxide / nano silver composite antibacterial and antiviral material.

[0109] By detecting, the silver in the components of the polyaniline graphene / graphene oxide / nano silver composite antibacterial and antiviral material accounts for about 10 parts, the graphene oxide accounts for about 45 parts, and the polyaniline graphene accounts for about 45 parts. When the composite antibacterial and antiviral material is added to the waterborne alkyd topcoat according to 0.2% of the components, the antibacterial rate can reach 99.99%, the antiviral rate against H3N2 virus can reach 99.99%, and the antiviral rate against enterovirus 71 can reach 96.25%.

[0110] Example 5

[0111] A preparation method of a polyaniline graphene / graphene oxide / nano copper-nano silver composite antibacterial and antiviral material includes the following steps:

[0112] (1) Mix graphene with polyvinylpyrrolidone at a concentration of 15 g / L in an aqueous solution and ultrasonicate at a power of 960 KW for 8 h to obtain 500 mL of a uniformly dispersed graphene solution. Then adjust the pH value to 2 with concentrated phosphoric acid. Then add 7.5 g of aniline and place the graphene solution in an ice bath.

[0113] (2) Dissolve 30 g of ammonium persulfate in phosphoric acid, slowly drop it into the graphene solution containing aniline obtained in step (1) in an ice bath, and react at 0 °C for 12 h. Then repeatedly wash by centrifugation until the pH is neutral to obtain a polyaniline-modified graphene solution.

[0114] (3) Ultrasonicate graphite oxide in an aqueous solution at a concentration of 15 g / L at a power of 960 KW for 8 h to obtain 500 mL of a uniformly dispersed graphene oxide solution.

[0115] (4) Prepare 500 mL of an aqueous solution of anhydrous copper sulfate at a concentration of 1.5 g / L. After stirring the anhydrous copper sulfate solution evenly, add 0.75 g of potassium nitrate and continue to stir to prepare a complex solution, and adjust the pH value to neutral with NaOH. Then stir the graphene oxide solution, the polyaniline graphene solution and the complex solution evenly to prepare an electrolyte; among them, the mass ratio of polyaniline graphene to graphene oxide is 1:1; place a copper plate as the anode and cathode in the electrolyte, connect the power supply, and electroplate for 0.1 h. Scrape off the deposit on the cathode plate.

[0116] (5) Prepare 500 mL of silver nitrate aqueous solution with a concentration of 1.5 g / L. After stirring the silver nitrate solution evenly, add 0.75 g of potassium nitrate and continue to stir to prepare a complex solution, and adjust the pH value to neutral with NaOH. Then stir the graphene oxide solution, polyaniline-graphene solution and complex solution evenly to prepare an electrolyte; wherein, the mass ratio of polyaniline-graphene to graphene oxide is 1:1; Place silver plates as the anode and cathode in the electrolyte, connect the power supply, and electroplate for 0.1 h. Scrape off the deposit on the cathode plate.

[0117] (6) Scrape off the deposits on the cathode plates in steps (4) and (5), add ammonia water to adjust the pH to neutral, then add 7.5 g of ethylenediamine and react at 30 °C for 4 hours. Then repeatedly wash by centrifugation with clear water until the pH is about 8. Then freeze-dry at -20 °C for 48 h to obtain the polyaniline-graphene / graphene oxide / nano-copper-nano-silver composite antibacterial and antiviral material.

[0118] By detecting, in the components of the polyaniline-graphene / graphene oxide / nano-copper-nano-silver composite antibacterial and antiviral material, copper accounts for about 1.0 part, silver accounts for about 1.0 part, graphene oxide accounts for about 50 parts, and polyaniline-graphene accounts for about 50 parts. When this composite antibacterial and antiviral material is added to the waterborne polyurethane topcoat according to 0.2% of the components, the antibacterial rate can reach 99.99%, the antiviral rate against H3N2 virus can reach 99.99%, and the antiviral rate against enterovirus 71 can reach 97.51%.

[0119] Comparative Example 1:

[0120] This comparative example provides a preparation method of a polyaniline-graphene nano-copper composite material:

[0121] (1) Mix graphene in an aqueous solution with a concentration of 0.1 g / L and polyvinylpyrrolidone with a concentration of 0.01 g / L, and ultrasonicate at a power of 240 KW for 0.5 h to obtain 500 mL of a uniformly dispersed graphene solution. Then adjust the pH value to 4 with concentrated phosphoric acid, add 0.5 g of aniline, and then place the graphene solution in an ice bath.

[0122] (2) Dissolve 1 g of ammonium persulfate in phosphoric acid, slowly drop it into the aniline-containing graphene solution obtained in step (1) in an ice bath, and react at 10 °C for 6 h. Then repeatedly wash the pH to neutral by centrifugation to obtain a polyaniline-modified graphene solution.

[0123] (3) Prepare 500 mL of anhydrous copper sulfate aqueous solution with a concentration of 0.1 g / L. After stirring the anhydrous copper sulfate solution evenly, add 0.2 g of potassium nitrate and continue to stir to prepare a complex solution, and adjust the pH value to neutral with NaOH. Then stir the polyaniline-graphene solution and the complex solution evenly to prepare an electrolyte.

[0124] (4) Place copper plates as the anode and cathode in the electrolyte solution, connect the power supply, and electroplate for 2 h. Scrape off the deposits on the cathode plate, and then repeatedly wash by centrifugation with pure water until the pH is about 8. Then freeze-dry at -30 °C for 12 h to obtain the polyaniline graphene nano-copper composite material.

[0125] Comparative Example 2:

[0126] (1) Ultrasonicate graphite oxide in an aqueous solution at a concentration of 0.1 g / L with a power of 240 KW for 0.5 h to obtain 500 mL of a uniformly dispersed graphene oxide solution.

[0127] (2) Prepare 500 mL of an aqueous solution of anhydrous copper sulfate at a concentration of 0.1 g / L. After stirring the anhydrous copper sulfate solution evenly, add 0.2 g of potassium nitrate and continue stirring to prepare a complex solution, and adjust the pH value to neutral with NaOH. Then stir the graphene oxide solution and the complex solution evenly to prepare the electrolyte solution.

[0128] (3) Place copper plates as the anode and cathode in the electrolyte solution, connect the power supply, and electroplate for 2 h. Scrape off the deposits on the cathode plate, add ammonia water to adjust the pH to neutral, then add 0.2 g of ethylenediamine, and react at 90 °C for 0.1 h. Then repeatedly wash by centrifugation with pure water until the pH is about 8. Then freeze-dry at -30 °C for 12 h to obtain the graphene oxide / nano-copper composite material.

[0129] Comparative Example 3:

[0130] (1) Mix graphene in an aqueous solution at a concentration of 0.1 g / L with 0.01 g / L of polyvinylpyrrolidone, and ultrasonicate with a power of 240 KW for 0.5 h to obtain 500 mL of a uniformly dispersed graphene solution. Then adjust the pH value to 4 with concentrated phosphoric acid, and then add 0.5 g of aniline and place the graphene solution in an ice bath.

[0131] (2) Dissolve 1 g of ammonium persulfate in phosphoric acid, and slowly drip it into the graphene solution containing aniline obtained in step (1) in an ice bath and react at 10 °C for 6 h. Then repeatedly wash by centrifugation to wash the pH to neutral to obtain the polyaniline-modified graphene solution.

[0132] (3) Ultrasonicate graphite oxide in an aqueous solution at a concentration of 0.1 g / L with a power of 240 KW for 0.5 h to obtain 500 mL of a uniformly dispersed graphene oxide solution.

[0133] (4) Prepare 500 mL of an aqueous solution of anhydrous copper sulfate at a concentration of 0.1 g / L. After stirring the anhydrous copper sulfate solution evenly, add 0.2 g of potassium nitrate and continue stirring to prepare a complex solution, and adjust the pH value to neutral with NaOH. Then configure a 500 mL mixed solution by mixing graphene oxide and polyaniline graphene in a mass ratio of 9:1 and stir evenly with the complex solution to prepare the electrolyte solution.

[0134] (5) Place copper plates as the anode and cathode in the electrolyte solution, connect the power supply, and electroplate for 2 h. Scrape off the deposit on the cathode plate, add ammonia water to adjust the pH to neutral, then add 0.2 g of ethylenediamine and react at 90 °C for 0.1 h. Then repeatedly wash by centrifugation with clear water until the pH is about 8. Then freeze-dry at -30 °C for 12 h to obtain the polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material.

[0135] Comparative Example 4:

[0136] (1) Disperse graphene in an aqueous solution at a concentration of 0.1 g / L with 0.01 g / L of polyvinylpyrrolidone, and ultrasonicate at a power of 240 KW for 0.5 h to obtain 500 mL of a uniformly dispersed graphene solution. Then adjust the pH value to 4 with concentrated phosphoric acid, add 0.5 g of aniline, and then place the graphene solution in an ice bath.

[0137] (2) Dissolve 1 g of ammonium persulfate in phosphoric acid, slowly drop it into the graphene solution containing aniline obtained in step (1) in an ice bath, and react at 10 °C for 6 h. Then repeatedly wash by centrifugation to wash the pH to neutral to obtain a polyaniline-modified graphene solution.

[0138] (3) Disperse graphene oxide in an aqueous solution at a concentration of 0.1 g / L, and ultrasonicate at a power of 240 KW for 0.5 h to obtain 500 mL of a uniformly dispersed graphene oxide solution.

[0139] (4) Prepare 500 mL of an aqueous solution of anhydrous copper sulfate at a concentration of 0.1 g / L. After stirring the anhydrous copper sulfate solution evenly, add 0.2 g of potassium nitrate and continue to stir to prepare a complex solution, and adjust the pH value to neutral with NaOH. Then configure a 500 mL mixed solution with the mass ratio of graphene oxide to polyaniline graphene of 1:9 and stir evenly with the complex solution to prepare an electrolyte solution.

[0140] (5) Place copper plates as the anode and cathode in the electrolyte solution, connect the power supply, and electroplate for 2 h. Scrape off the deposit on the cathode plate, add ammonia water to adjust the pH to neutral, then add 0.2 g of ethylenediamine and react at 90 °C for 0.1 h. Then repeatedly wash by centrifugation with clear water until the pH is about 8. Then freeze-dry at -30 °C for 12 h to obtain the polyaniline graphene / graphene oxide / nano-copper composite antibacterial and antiviral material.

[0141] Comparative Example 5:

[0142] (1) Disperse graphene in an aqueous solution at a concentration of 0.1 g / L with 0.01 g / L of polyvinylpyrrolidone, and ultrasonicate at a power of 240 KW for 0.5 h to obtain 500 mL of a uniformly dispersed graphene solution. Then adjust the pH value to 4 with concentrated phosphoric acid, add 0.5 g of aniline, and then place the graphene solution in an ice bath.

[0143] (2) Dissolve 1 g of ammonium persulfate in phosphoric acid, and slowly add it dropwise to the graphene solution containing aniline obtained in step (1) in an ice bath, and react at 10 °C for 6 h. Then repeatedly wash by centrifugation until the pH is washed to neutral to obtain a polyaniline-modified graphene solution;

[0144] (3) Prepare 500 mL of an aqueous solution of anhydrous copper sulfate at a concentration of 0.1 g / L. After stirring the anhydrous copper sulfate solution evenly, add 0.2 g of potassium nitrate and continue to stir to prepare a complex solution, and adjust the pH value to neutral with NaOH. Then stir evenly the graphene solution prepared by the reduction method purchased from Shandong Hengli Graphene Technology Co., Ltd., the polyaniline graphene solution and the complex solution to prepare an electrolyte solution.

[0145] (4) Place copper plates as the anode and cathode in the electrolyte solution, connect the power supply, and electroplate for 2 h. Scrape off the deposit on the cathode plate, add ammonia water to adjust the pH to neutral, then add 0.2 g of ethylenediamine and react at 90 °C for 0.1 h. Then repeatedly wash by centrifugation with clear water until the pH is about 8. Then freeze-dry at -30 °C for 12 h to obtain the polyaniline graphene / graphene / nano-copper composite material.

[0146] Comparative Example 6:

[0147] (1) Add 10 g of expanded graphite powder and aniline monomer to 1 L of N-methylpyrrolidone solution, ultrasonically stir evenly, and then inject it into a high-pressure reaction kettle. After heating the reaction kettle to 120 °C, introduce carbon dioxide into the reaction kettle to make the air pressure reach 20 MPa and react for 1 h.

[0148] (2) After the reaction is completed, release the air pressure and take out the material. Add hydrochloric acid with a concentration of 0.5 mol / L to the material, stir evenly, and then add 5 g of polyvinylpyrrolidone. Then add 1 mol / L of hydrogen peroxide and react for 2 h under ice bath conditions. After repeatedly centrifuging, washing and freeze-drying the reaction product, polyaniline graphene is obtained.

[0149] (3) Oxidize graphite in an aqueous solution at a concentration of 0.1 g / L and ultrasonically treat it at a power of 240 KW for 0.5 h to obtain 500 mL of a uniformly dispersed graphene oxide solution.

[0150] (4) Prepare 500 mL of an aqueous solution of anhydrous copper sulfate at a concentration of 0.1 g / L. After stirring the anhydrous copper sulfate solution evenly, add 0.2 g of potassium nitrate and continue to stir to prepare a complex solution, and adjust the pH value to neutral with NaOH. Then mix the graphene oxide solution and the polyaniline graphene solution in a ratio of 1:1 to prepare a 500 mL mixed solution, and stir evenly with the complex solution to prepare an electrolyte solution.

[0151] (5) Place copper plates as the anode and cathode in the electrolyte, connect the power supply, and electroplate for 2 h. Scrape off the deposits on the cathode plate, add ammonia water to adjust the pH to neutral, then add 0.2 g of ethylenediamine and react at 90 °C for 0.1 h. Then repeatedly wash by centrifugation with clear water until the pH is about 8. Then freeze-dry at -30 °C for 12 h to obtain the polyaniline graphene / graphene oxide / nano-copper composite material.

[0152] Refer to GB / T21866-2008 and T / CNCIA 03002-2020 to conduct antibacterial, antiviral, water resistance, acid and alkali resistance tests on Examples 1-5 and Comparative Examples 1-6. Among them, the substrate for the water resistance, acid and alkali resistance performance test is 20# seamless steel plate with manual rust removal to St2 level, and the coating is a one-component waterborne polyurethane varnish with a polyaniline graphene / graphene oxide / nano-copper composite material addition of 0.2%, and the thickness is 60 μm. The corresponding test results are shown in Table 1. The test results in this Table 1 are the average values of the test results of multiple batches of products.

[0153] Table 1 Test results of product performance of Examples 1-5 and Comparative Examples 1-6

[0154]

[0155] In addition, the inventor of this case also referred to the foregoing examples, and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and all obtained relatively ideal results.

[0156] It should be understood that the technical solution of the present invention is not limited to the limitations of the above specific implementation cases. Any technical deformation made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope protected by the claims falls within the protection scope of the present invention.

Claims

1. A composite antibacterial and antiviral material, characterized in that, Comprising: Polyaniline graphene, graphene oxide and nano metal; wherein the polyaniline graphene and graphene oxide are arranged alternately and parallelly, and the nano metal is uniformly and neatly distributed between the layers of the polyaniline graphene and graphene oxide, so that the layers of the polyaniline graphene, the graphene oxide layers and the nano metal form a "labyrinth structure", and the nano metal includes nano copper and / or nano silver; The preparation method of the composite antibacterial and antiviral material comprises: Mixing copper sulfate and / or silver nitrate, potassium nitrate and water evenly, and adjusting the pH value of the obtained solution to 8-10 to obtain a complex solution; then mixing the graphene oxide dispersion, polyaniline graphene and the complex solution evenly to obtain an electrolyte solution; And constructing an electrochemical reaction system with the electrolyte solution, the cathode and the anode, and using an electrodeposition technique to deposit a polyaniline graphene / graphene oxide / nano metal material on the surface of the cathode, so as to obtain a composite antibacterial and antiviral material.

2. The composite antibacterial and antiviral material according to claim 1, wherein The raw materials of the composite antibacterial and antiviral material include the following components calculated by mass percentage: 35-50% polyaniline graphene, 35-50% graphene oxide, 1-30% nano metal.

3. The composite antibacterial and antiviral material according to claim 1, characterized in that: The diameter of the polyaniline modified graphene is 0.1-50 μm, and the number of layers is 1-50 layers; And / or, the diameter of the graphene oxide is 0.1-50 μm, and the number of layers is 1-50 layers; And / or, the particle size of the nano metal is 3-500 nm.

4. The composite antibacterial and antiviral material according to claim 1, characterized in that: The antiviral rate of the composite antibacterial and antiviral material against influenza A virus H3N2 is above 99.90%; And / or, the antiviral rate of the composite antibacterial and antiviral material against enterovirus 71 is above 95.00%; And / or, the antibacterial rate of the composite antibacterial and antiviral material against Escherichia coli is above 99.99%; And / or, the antibacterial rate of the composite antibacterial and antiviral material against Staphylococcus aureus is above 99.99%.

5. A preparation method of a composite antibacterial and antiviral material, characterized in that, Comprising: Providing a dispersion liquid containing polyaniline graphene, graphene oxide, copper sulfate and / or silver nitrate as an electrolyte solution; And constructing an electrochemical reaction system with the electrolyte solution, the cathode and the anode, and using an electrodeposition technique to deposit a polyaniline graphene / graphene oxide / nano metal material on the surface of the cathode, so as to obtain a composite antibacterial and antiviral material.

6. The preparation method according to claim 5, characterized in that Comprising: Mixing copper sulfate and / or silver nitrate, potassium nitrate and water evenly, and adjusting the pH value of the obtained solution to 8-10 to obtain a complex solution; And mixing the graphene oxide dispersion, polyaniline graphene and the complex solution evenly to obtain the electrolyte solution.

7. The preparation method according to claim 6, characterized in that: The mass ratio of the copper sulfate and / or silver nitrate to potassium nitrate is 1:1-4; The mass ratio of the copper sulfate and / or silver nitrate to graphene oxide in the electrolyte solution is 1:1-10; The mass ratio of the polyaniline graphene to graphene oxide in the electrolyte solution is 1-2:1-2.

8. The preparation method according to claim 5, characterized in that: The time for depositing the polyaniline graphene / graphene oxide / nano metal material on the surface of the cathode by using the electrodeposition technique is 0.5-2 h.

9. The preparation method according to claim 5, characterized in that: The cathode and the anode are independently selected from a copper electrode or a silver electrode.

10. The preparation method according to claim 5, characterized in that, Also comprising: The polyaniline graphene / graphene oxide / nano-metal material is placed in ammonia water and stirred and reacted with ethylenediamine at 30-90 °C, and then obtained a composite antibacterial and antiviral material after washing and drying treatments.

11. The preparation method according to claim 10, characterized in that: The mass ratio of the ethylenediamine to the graphene oxide is 1:1-4; the drying treatment method is selected from freeze-drying, the temperature of the freeze-drying is -30~-20 °C, the time is 12-48 h; the stirring reaction time is 1-4 h.

12. The preparation method according to claim 5, characterized in that, It also includes: Reacting a mixed reaction system containing graphene, aniline and an initiator at 0-10 °C to obtain polyaniline graphene.

13. The preparation method according to claim 12, characterized in that: The initiator is selected from ammonium persulfate; the mass ratio of the graphene, aniline and the initiator is 1-5:10-20:

20.

14. A composite antibacterial and antiviral material prepared by the preparation method according to any one of claims 5-13.

15. An antibacterial and antiviral product, characterized in that At least including the composite antibacterial and antiviral material according to any one of claims 1-4, 14.

16. A coating composition comprising a base coating, characterized in that, It also includes the composite antibacterial and antiviral material according to any one of claims 1-4, 14.

17. The coating composition according to claim 16, wherein: The base coating is selected from any one or a combination of two or more of waterborne polyurethane, waterborne acrylic, waterborne alkyd, waterborne fluorocarbon, waterborne epoxy, waterborne silicone, and waterborne inorganic coatings.

18. The coating composition according to claim 16, wherein: The content of the composite antibacterial and antiviral material in the coating composition is 0.1-2 wt%.

Images