A composite nano zinc oxide antibacterial agent, preparation method and application thereof

Abstract

The present invention provides a composite nano zinc oxide antibacterial agent, a preparation method and its application. The composite nano zinc oxide antibacterial agent comprises, by mass percentage, 20-40% modified nano zinc oxide, 8-12% eugenol, 20-30% distilled water, and the balance is anhydrous ethanol; the modified nano zinc oxide is nano zinc oxide cross-linked and modified with gallic acid and citric acid. The modified nano zinc oxide can effectively enhance the antibacterial properties of the composite nano zinc oxide antibacterial agent, while not using inorganic antibacterial agents such as titanium dioxide and silver ions, thereby effectively reducing the cost of the modified nano zinc oxide antibacterial agent; the nano zinc oxide modified with gallic acid and citric acid is used in combination with eugenol, which greatly enhances the antibacterial effect and antibacterial time of the composite nano zinc oxide antibacterial agent, and is more conducive to industrialization.

Description

Technical Field

[0001] The invention relates to the technical field of zinc oxide active agents, and in particular to a composite nano zinc oxide antibacterial agent, a preparation method and application thereof. Background Art

[0002] Nano zinc oxide has extremely high chemical activity and excellent catalytic and photocatalytic activity, and has anti-infrared, ultraviolet radiation and sterilization functions; it is used as a catalytic material and a semiconductor material for photochemistry, and can catalyze the photolysis of organic molecules; nano zinc oxide has a large specific surface area and stronger activity, and can be used as a functional additive such as a vulcanizing activator. Nano zinc oxide is widely used in plastic products as an inorganic antibacterial material.

[0003] Patent (CN113462028B) discloses a nano antibacterial agent for plastics, specifically relates to the field of plastic processing technology, and comprises the following raw materials: silver-loaded titanium dioxide, modified nano zinc oxide, antibacterial liquid, coupling agent, zeolite powder, silver chloride and alkaline amino acid. The present invention loads silver ions on titanium dioxide, and uses quaternary ammonium salt solution to modify nano zinc oxide, embeds silver-loaded titanium dioxide and modified nano zinc oxide into zeolite powder with nano holes, can prevent silver ions from precipitating from water, slow down the reduction of antibacterial properties of plastics, silver-loaded titanium dioxide can enhance the photocatalytic antibacterial effect of plastics, and make the overall antibacterial effect of plastics better, and use quaternary ammonium salt to accommodate nano zinc oxide for modification so that the antibacterial effect of plastics is better, and by adding silver chloride and alkaline amino acid, the antibacterial properties of plastics can be improved while the dispersion effect of nano antibacterial agent in plastic particles can be better.

[0004] Although nano zinc oxide is used in the nano antibacterial agent in the above patent document, the content of nano zinc oxide is not high. Silver-loaded titanium dioxide, silver chloride, etc. play a greater antibacterial role, and the cost of the antibacterial agent is higher.

[0005] Another type of antibacterial material is natural antibacterial agents, which are mainly extracted from natural plants, such as eugenol, mustard, castor oil, horseradish, etc. They are easy to use, but have limited antibacterial effects, poor heat resistance, low bactericidal rates, cannot be used for a long time, and are in small quantities. After long-term use, their antibacterial activity will gradually decrease, affecting the antibacterial effect of the material itself, so their industrialization prospects are slim. In view of this, we proposed a composite nano zinc oxide antibacterial agent and its preparation method. Summary of the invention

[0006] Purpose of the invention: In order to overcome the problem of poor antibacterial effect of existing nano zinc oxide antibacterial agents used as rubber additives, natural antibacterial agents are compounded to overcome the problems of short antibacterial time and low antibacterial activity of natural antibacterial agents, and to provide a composite nano zinc oxide antibacterial agent, a preparation method and its application.

[0007] The technical solution of the present invention:

[0008] On the one hand, the present application provides a composite nano zinc oxide antibacterial agent, which comprises, by mass percentage:

[0009]

[0010] A composite nano zinc oxide antibacterial agent, measured by mass percentage, comprises:

[0011]

[0012] In some embodiments, the modified nano zinc oxide is nano zinc oxide cross-linked and modified with gallic acid and citric acid.

[0013] In some embodiments, the preparation method of the modified nano zinc oxide comprises:

[0014] Step 1: adding nano zinc oxide to a deionized water / ethanol mixed solution, and ultrasonically treating the solution to obtain solution 1; dissolving gallic acid in the deionized water / ethanol mixed solution, and adjusting the pH of the solution to 7-8 to obtain solution 2; mixing solution 1 and solution 2, stirring and reacting, to obtain an intermediate product;

[0015] Step 2: adding the intermediate product to a deionized water / ethanol mixed solution, and ultrasonically treating the solution to obtain solution 3; dissolving citric acid in the deionized water / ethanol mixed solution to obtain solution 4; mixing solution 3 and solution 4, adding concentrated sulfuric acid to heat and react, and obtaining modified nano zinc oxide.

[0016] In some embodiments, the molar ratio of the nano zinc oxide, gallic acid, and citric acid is 1:6-7:6-21.

[0017] In some embodiments, the molar ratio of nano zinc oxide, gallic acid, and citric acid is 1:6:15.

[0018] In some embodiments, the reaction temperature of the mixed stirring reaction is 30-42° C., and the reaction time is 2-4 h.

[0019] In some embodiments, the reaction temperature of the heating reaction is 100-110° C., and the reaction time is 2-4 hours.

[0020] Nano zinc oxide modified by gallic acid and citric acid not only brings the antibacterial properties of gallic acid itself, but also cross-links to form a network structure, reducing the influence of external factors on nano zinc dioxide and prolonging its antibacterial activity.

[0021] On the other hand, the present application also provides a method for preparing the composite nano zinc oxide antibacterial agent, comprising:

[0022] Weigh the modified nano zinc oxide and eugenol, add them to anhydrous ethanol, stir magnetically for 10-20 minutes, then add distilled water dropwise, ultrasonically treat for 10-20 minutes, then heat in a vacuum drying oven, keep warm for 8-12 hours, and naturally cool to room temperature to obtain a composite nano zinc oxide antibacterial agent.

[0023] An antibacterial resin, the raw material of which includes the composite nano zinc oxide antibacterial agent.

[0024] Beneficial effects:

[0025] The composite nano zinc oxide antibacterial agent of the present invention can effectively enhance the antibacterial performance, and does not use inorganic antibacterial agents such as titanium dioxide and silver ions, thereby effectively reducing the cost of the modified nano zinc oxide antibacterial agent; the nano zinc oxide is modified with gallic acid and citric acid, and is used in combination with eugenol, which greatly enhances the antibacterial effect and antibacterial time of the composite nano zinc oxide antibacterial agent, and is more conducive to industrialization. DETAILED DESCRIPTION

[0026] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0027] Unless otherwise specified, the chemical reagents used in the present invention are all commercially available analytically pure.

[0028] Nano zinc oxide was purchased from high-purity 3N nano zinc oxide powder from Hangzhou Hengna New Materials Co., Ltd. Model: HN-JH03. Eugenol CAS: 97-53-0.

[0029] Preparation of modified nano zinc oxide 1

[0030] Step 1: Add 1 mol of nano zinc oxide to 10 ml of deionized water / ethanol (8:2 v / v) solution, and ultrasonically treat for 1 h to obtain solution 1; dissolve 6 mol of gallic acid in 10 ml of deionized water / ethanol (8:2 v / v) solution, and adjust the pH of the solution to 7 to obtain solution 2; add solution 2 dropwise to solution 1, stir at a constant temperature of 40° C. for 3 h, and rotate at 600 r / min, and mix and stir to react to obtain an intermediate product;

[0031] Step 2: The intermediate product was added to 10 ml of deionized water / ethanol (8:2 v / v) solution and ultrasonically treated for 1 h to obtain solution 3; 6 mol of citric acid was dissolved in 10 ml of deionized water / ethanol (8:2 v / v) solution to obtain solution 4; solution 3 and solution 4 were mixed, 1 mol of concentrated sulfuric acid was added and heated to 100°C for reaction, and modified nano zinc oxide (hereinafter referred to as modified nanoZnO) was obtained after the reaction was completed.

[0032] Preparation of modified nano zinc oxide 2

[0033] The preparation method is similar to that of modified nano zinc oxide 1, except that the added molar amounts of gallic acid and citric acid are 6 mol and 15 mol, respectively, to obtain modified nano zinc oxide 2.

[0034] Preparation of modified nano zinc oxide 3

[0035] The preparation method is similar to that of modified nano zinc oxide 1, except that the added molar amounts of gallic acid and citric acid are 6 mol and 21 mol, respectively, to obtain modified nano zinc oxide 3.

[0036] Preparation of modified nano zinc oxide 4

[0037] The preparation method is similar to that of modified nano zinc oxide 1, except that the added molar amounts of gallic acid and citric acid are 7 mol and 21 mol, respectively, to obtain modified nano zinc oxide 4.

[0038] Preparation of modified nano zinc oxide 5

[0039] The preparation method is similar to that of modified nano zinc oxide 1, except that the added molar amounts of gallic acid and citric acid are 0 mol and 12 mol, respectively, to obtain modified nano zinc oxide 5.

[0040] Preparation of modified nano zinc oxide 6

[0041] The preparation method is similar to that of modified nano zinc oxide 1, except that the added molar amounts of gallic acid and citric acid are 12 mol and 0 mol, respectively, to obtain modified nano zinc oxide 6.

[0042] The antibacterial agents of the embodiments and comparative examples were prepared according to the mass percentage of each component shown in Table 1.

[0043] Table 1 Components of Examples and Comparative Examples

[0044]

[0045] Note: In the above table, "L" represents an example, such as "L1" represents Example 1; "D" represents a comparative example, such as "D1" represents Comparative Example 1.

[0046] The antibacterial agents in the comparative examples and embodiments of the present invention were tested.

[0047] Weigh 100 parts of natural rubber, 5.0 parts of the above antibacterial agent, 2.0 parts of accelerator DM, and 3 parts of sulfur according to mass; use a 500mL internal mixer to prepare the mixed rubber. Mixing process conditions: starting temperature 60℃, rotor speed 77r·min -1 ; First, add natural rubber and plasticize for 1 minute, then add antibacterial agent and plasticize for 2 minutes, add DM and sulfur and plasticize for 3 minutes, after rubber discharge, roll on the open mill without roller (roller distance 0.2mm, front roller temperature (55±1)℃, rear roller (50±1)℃); adjust the roller distance to 2mm to produce the sheet, mark it and park it for use. Vulcanized rubber sample preparation: Use a flat vulcanizer to prepare the vulcanized test piece. Vulcanization conditions: 143℃×10MPa×t c90 Then the antibacterial rate of the vulcanized test piece was tested. During the test, the antibacterial rate of the newly produced vulcanized test piece was tested. Then the selected vulcanized test piece was immersed in water for 30 days and then the antibacterial rate was tested. The test results of the antibacterial agent are shown in Table 2.

[0048] Table 2 Test results of antimicrobial agents

[0049]

[0050] It can be seen from the experimental results in the above table that the composite nano zinc oxide antibacterial agent of the present invention can effectively enhance the antibacterial performance, and does not use inorganic antibacterial agents such as titanium dioxide and silver ions, thereby effectively reducing the cost of the modified nano zinc oxide antibacterial agent. By comparing the embodiment with comparative examples 7-8, it can be seen that the use of gallic acid and citric acid to modify nano zinc oxide can effectively enhance the antioxidant function of nano zinc oxide, and its use in combination with eugenol can greatly enhance the antibacterial effect and antibacterial time of the composite nano zinc oxide antibacterial agent, which is more conducive to industrial use.

[0051] The present invention can also have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims attached to the present invention.

Claims

1. A composite nano zinc oxide antibacterial agent, characterized in that: In terms of mass percentage, it includes: Modified nano zinc oxide 20-40%; Eugenol 8-12%; Distilled water 20-30%; Anhydrous ethanol residue; The modified nano zinc oxide is nano zinc oxide cross-linked and modified with gallic acid and citric acid; The preparation method of the modified nano zinc oxide comprises: Step 1: adding nano zinc oxide to a deionized water / ethanol mixed solution, and ultrasonically treating the solution to obtain solution 1; dissolving gallic acid in the deionized water / ethanol mixed solution, and adjusting the pH of the solution to 7-8 to obtain solution 2; mixing solution 1 and solution 2, stirring and reacting, to obtain an intermediate product; Step 2: adding the intermediate product to a deionized water / ethanol mixed solution, and ultrasonically treating the solution to obtain solution 3; dissolving citric acid in the deionized water / ethanol mixed solution to obtain solution 4; mixing solution 3 and solution 4, adding concentrated sulfuric acid to heat and react, and obtaining modified nano zinc oxide.

2. The composite nano zinc oxide antibacterial agent according to claim 1, characterized in that: In terms of mass percentage, it includes: Modified nano zinc oxide 25-35%; Eugenol 8-10%; Distilled water 20-30%; Anhydrous ethanol balance.

3. The composite nano zinc oxide antibacterial agent according to claim 1, characterized in that: The reaction temperature of the mixed stirring reaction is 30-42° C., and the reaction time is 2-4 hours.

4. The composite nano zinc oxide antibacterial agent according to claim 1, characterized in that: The reaction temperature of the heating reaction is 100-110° C., and the reaction time is 2-4 hours.

5. The composite nano zinc oxide antibacterial agent according to claim 1, characterized in that: The molar ratio of the nano zinc oxide, gallic acid and citric acid is 1:6-7:6-21.

6. The composite nano zinc oxide antibacterial agent according to claim 5, characterized in that: The molar ratio of the nano zinc oxide, gallic acid and citric acid is 1:6:

15.

7. The composite nano zinc oxide antibacterial agent according to any one of claims 1 to 6, characterized in that: include: Weigh the modified nano zinc oxide and eugenol, add them to anhydrous ethanol, stir magnetically for 10-20 minutes, then add distilled water dropwise, ultrasonically treat for 10-20 minutes, then heat in a vacuum drying oven, keep warm for 8-12 hours, and naturally cool to room temperature to obtain a composite nano zinc oxide antibacterial agent.

8. An antibacterial resin, wherein the raw material of the antibacterial resin comprises the composite nano zinc oxide antibacterial agent according to any one of claims 1 to 6.

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