Antibacterial deodorant and preparation method thereof

Abstract

The invention relates to the technical field of deodorants, in particular to an antibacterial deodorant and a preparation method thereof. The antibacterial deodorant is prepared from a stearic acid modified melamine-formaldehyde prepolymer, a silver modified melamine-formaldehyde prepolymer and calcium carbonate through emulsion suspension polymerization. The stearic acid modified melamine-formaldehyde prepolymer is obtained by mixing modified melamine synthesized by melamine and stearoyl chloride with a formaldehyde aqueous solution, and the silver modified melamine-formaldehyde prepolymer is obtained by mixing silver amide particles with the formaldehyde aqueous solution. The antibacterial deodorant prepared by the invention has an efficient deodorization effect and excellent antibacterial performance.

Description

Technical Field

[0001] The present invention relates to the technical field of deodorants, in particular to an antibacterial deodorant and a preparation method thereof. Background Art

[0002] With the rapid growth in the number of pets, the problem of pet feces disposal has gradually become an important challenge to urban environmental management and family hygiene. During the decomposition process, pet feces will release a large amount of foul-smelling gases, such as hydrogen sulfide, ammonia and other volatile organic compounds. These gases will not only pollute the air quality, but also have adverse effects on the health of pet owners and people in the surrounding environment. In addition, pet feces contain a large number of pathogens, such as Escherichia coli and Salmonella, which can be transmitted through the air or contact, increasing the risk of disease transmission, especially in multi-pet households or environments where pets are kept together. The problem is particularly prominent.

[0003] At present, the common pet feces deodorization products on the market mainly include chemical deodorants, physical adsorbents and biological enzyme preparations. However, these products have certain limitations in practical applications. For example, although chemical deodorants can quickly neutralize some malodorous gases, there may be chemical residues, which may cause potential harm to pets and the environment; although physical adsorbents (such as activated carbon) have certain adsorption capacity, the adsorption efficiency is limited, and the removal speed of malodorous gases is slow; biological enzyme preparations require a long reaction time and are difficult to meet the needs of rapid deodorization. In addition, most of these products lack antibacterial properties and cannot effectively inhibit the growth of pathogens in pet feces, making it difficult to balance deodorization effect and hygiene performance. Summary of the invention

[0004] In view of this, the purpose of the present invention is to provide an antibacterial deodorant and a preparation method thereof, so as to efficiently remove malodorous gases, improve the breeding environment, and ensure the healthy growth of pets.

[0005] Based on the above purpose, the present invention provides a method for preparing an antibacterial deodorant, comprising the following steps: (1) Add melamine and stearyl chloride to N,N-dimethylformamide, raise the temperature to 75-85°C, stir and react for 4-6 hours, and rotary evaporate to obtain modified melamine; (2) adding the modified melamine to a 37 wt % formaldehyde aqueous solution, heating the solution to 75-85° C., and stirring for 20-40 min to obtain a stearic acid modified melamine-formaldehyde prepolymer; (3) adding silver nitrate and ethylenediamine to deionized water, cooling to 0-5°C, stirring for 20-40 minutes, then adding a 5wt% sodium borohydride aqueous solution, stirring for 4-6 minutes, centrifuging, washing with water, and vacuum drying to obtain silver amide particles; (4) adding melamine and silver amide particles to a 37 wt % formaldehyde aqueous solution, heating to 75-85° C., and stirring for 20-40 min to obtain a silver-modified melamine-formaldehyde prepolymer; (5) Mixing stearic acid-modified melamine-formaldehyde prepolymer, silver-modified melamine-formaldehyde prepolymer and calcium carbonate, heating to 35-45° C., stirring for reaction for 0.5-1.5 h, adding liquid paraffin, heating to 80-90° C., stirring at a speed of 200-400 rpm for 1.5-2.5 h, standing for 20-28 h, centrifuging, washing, and vacuum drying to obtain resin microspheres; (6) The resin microspheres are placed in a muffle furnace, calcined at high temperature under a nitrogen atmosphere, washed with water, and vacuum dried to obtain an antibacterial deodorant.

[0006] Preferably, in step (1), the weight ratio of melamine, stearyl chloride and N,N-dimethylformamide is 10-15:7-11:80-120.

[0007] Preferably, in step (2), the weight ratio of the modified melamine to the 37 wt % formaldehyde aqueous solution is 15-25:10-30.

[0008] Preferably, in step (3), the weight ratio of silver nitrate, ethylenediamine, deionized water and 5 wt% sodium borohydride aqueous solution is 1:0.05-0.5:40-60:15-25.

[0009] Preferably, in step (4), the weight ratio of melamine, silver amide particles and 37 wt % formaldehyde aqueous solution is 4-6:0.3-0.8:2-3.

[0010] Preferably, in step (5), the ratio of stearic acid-modified melamine-formaldehyde prepolymer, silver-modified melamine-formaldehyde prepolymer, calcium carbonate and liquid paraffin is 30-50:6-10:3-8:400-600.

[0011] Preferably, the high temperature calcination in step (6) is as follows: heating from room temperature to 750-850°C at 2-4°C / min, keeping the temperature for 2-4h, and cooling to room temperature.

[0012] Furthermore, the present invention provides an antibacterial deodorant obtained by the preparation method of the antibacterial deodorant.

[0013] Beneficial effects of the present invention: The invention provides an antibacterial deodorant and a preparation method thereof. The removal effect of the antibacterial deodorant on malodorous gases such as hydrogen sulfide and ammonia and the antibacterial property thereof are significantly improved by using amide silver particles prepared by using stearyl chloride-modified melamine and ethylenediamine.

[0014] The stearyl chloride modified melamine prepared by the present invention optimizes the pore structure of the antibacterial deodorant by adjusting the cross-linking density with formaldehyde, so that hydrogen sulfide and ammonia can diffuse to the adsorption site more easily, thereby improving the removal efficiency of malodorous gases.

[0015] The silver amide particles prepared by using ethylenediamine in the present invention can be evenly dispersed in the matrix without blocking the pores, and more adsorption sites are provided, thereby further enhancing the adsorption capacity and catalytic decomposition efficiency of malodorous gases, and at the same time significantly improving the antibacterial performance.

[0016] The antibacterial deodorant of the present invention can effectively remove the malodorous gas generated by pet feces, improve air quality, and reduce the impact of malodor on the environment and personnel. In addition, its excellent antibacterial performance can inhibit the growth of pathogens, reduce the risk of disease transmission, and provide a strong guarantee for the healthy development of pets. DETAILED DESCRIPTION

[0017] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0018] Embodiment 1:

[0019] (1) Add 10 g of melamine and 7 g of stearyl chloride to 80 g of N,N-dimethylformamide, heat to 75 °C, stir and react for 4 h, and rotary evaporate to obtain modified melamine; (2) adding 15 g of modified melamine to 10 g of a 37 wt % formaldehyde aqueous solution, heating to 75 ° C, and stirring for 20 min to obtain a stearic acid modified melamine-formaldehyde prepolymer; (3) adding 1 g of silver nitrate and 0.05 g of ethylenediamine to 40 g of deionized water, cooling to 0°C, stirring for 20 min, then adding 15 g of a 5 wt% sodium borohydride aqueous solution, stirring for 5 min, centrifuging, washing with water, and vacuum drying to obtain amide silver particles; (4) adding 4 g of melamine and 0.3 g of silver amide particles to 2 g of a 37 wt % formaldehyde aqueous solution, heating to 75° C., and stirring for 20 min to obtain a silver-modified melamine-formaldehyde prepolymer; (5) 30 g of stearic acid-modified melamine-formaldehyde prepolymer, 6 g of silver-modified melamine-formaldehyde prepolymer and 3 g of calcium carbonate were mixed, the temperature was raised to 35° C., and the mixture was stirred for reaction for 0.5 h. Then 400 g of liquid paraffin was added, the temperature was raised to 80° C., and the mixture was stirred at a speed of 200 rpm for 1.5 h. The mixture was allowed to stand for 20 h, centrifuged, washed with petroleum ether, and vacuum dried to obtain resin microspheres. (6) The resin microspheres are placed in a muffle furnace, and the temperature is raised from room temperature to 750°C at a rate of 2°C / min in a nitrogen atmosphere, and the temperature is kept for 4 h. The microspheres are then cooled to room temperature, washed with water, and vacuum dried to obtain an antibacterial deodorant.

[0020] Embodiment 2:

[0021] (1) Add 12.6 g of melamine and 9.1 g of stearyl chloride to 100 g of N,N-dimethylformamide, raise the temperature to 80°C, stir and react for 5 h, and rotary evaporate to obtain modified melamine; (2) adding 20 g of modified melamine to 20 g of a 37 wt % formaldehyde aqueous solution, heating to 80° C., and stirring for 30 min to obtain a stearic acid-modified melamine-formaldehyde prepolymer; (3) adding 1 g of silver nitrate and 0.15 g of ethylenediamine to 50 g of deionized water, cooling to 0°C, stirring for 30 min, then adding 20 g of a 5 wt% sodium borohydride aqueous solution, stirring for 5 min, centrifuging, washing with water, and vacuum drying to obtain silver amide particles; (4) adding 5 g of melamine and 0.5 g of silver amide particles to 2.5 g of a 37 wt % formaldehyde aqueous solution, heating to 80° C., and stirring for 30 min to obtain a silver-modified melamine-formaldehyde prepolymer; (5) 40 g of stearic acid-modified melamine-formaldehyde prepolymer, 8 g of silver-modified melamine-formaldehyde prepolymer and 5 g of calcium carbonate were mixed, the temperature was raised to 40°C, and the mixture was stirred for reaction for 1 h. Then, 500 g of liquid paraffin was added, the temperature was raised to 85°C, and the mixture was stirred at 300 rpm for 2 h. The mixture was allowed to stand for 24 h, centrifuged, washed with petroleum ether, and vacuum dried to obtain resin microspheres. (6) The resin microspheres are placed in a muffle furnace, and the temperature is raised from room temperature to 800°C at a rate of 3°C / min under a nitrogen atmosphere, and the temperature is kept for 3 h. The microspheres are then cooled to room temperature, washed with water, and vacuum dried to obtain an antibacterial deodorant.

[0022] Embodiment 3:

[0023] (1) Add 15 g of melamine and 11 g of stearyl chloride to 120 g of N,N-dimethylformamide, heat to 85°C, stir and react for 6 h, and rotary evaporate to obtain modified melamine; (2) adding 25 g of modified melamine to 30 g of a 37 wt % formaldehyde aqueous solution, heating to 85° C., and stirring for 40 min to obtain a stearic acid-modified melamine-formaldehyde prepolymer; (3) adding 1 g of silver nitrate and 0.5 g of ethylenediamine to 60 g of deionized water, cooling to 5° C., stirring for 40 min, then adding 25 g of a 5 wt% sodium borohydride aqueous solution, stirring for 6 min, centrifuging, washing with water, and vacuum drying to obtain amide silver particles; (4) adding 6 g of melamine and 0.8 g of silver amide particles to 3 g of a 37 wt % formaldehyde aqueous solution, heating to 85° C., and stirring for 40 min to obtain a silver-modified melamine-formaldehyde prepolymer; (5) 50 g of stearic acid-modified melamine-formaldehyde prepolymer, 10 g of silver-modified melamine-formaldehyde prepolymer and 8 g of calcium carbonate were mixed, the temperature was raised to 45° C., and the mixture was stirred for reaction for 1.5 h. Then, 600 g of liquid paraffin was added, the temperature was raised to 90° C., and the mixture was stirred at 400 rpm for 2.5 h. The mixture was allowed to stand for 28 h, centrifuged, washed with petroleum ether, and vacuum dried to obtain resin microspheres. (6) The resin microspheres are placed in a muffle furnace, and the temperature is increased from room temperature to 850°C at a rate of 4°C / min in a nitrogen atmosphere, and the temperature is kept at that temperature for 2 h. The microspheres are then cooled to room temperature, washed with water, and vacuum dried to obtain an antibacterial deodorant.

[0024] Comparative Example 1: The difference between Comparative Example 1 and Example 2 is that the modified melamine in step (2) is replaced by melamine; (2) adding 20 g of melamine to 20 g of a 37 wt % formaldehyde aqueous solution, heating the solution to 80° C., and stirring the solution for 30 min to obtain a melamine-formaldehyde prepolymer; (3) adding 1 g of silver nitrate and 0.15 g of ethylenediamine to 50 g of deionized water, cooling to 0°C, stirring for 30 min, then adding 20 g of a 5 wt% sodium borohydride aqueous solution, stirring for 5 min, centrifuging, washing with water, and vacuum drying to obtain silver amide particles; (4) adding 5 g of melamine and 0.5 g of silver amide particles to 2.5 g of a 37 wt % formaldehyde aqueous solution, heating to 80° C., and stirring for 30 min to obtain a silver-modified melamine-formaldehyde prepolymer; (5) 40 g of melamine-formaldehyde prepolymer, 8 g of silver-modified melamine-formaldehyde prepolymer and 5 g of calcium carbonate were mixed, the temperature was raised to 40° C., and the mixture was stirred for reaction for 1 h. Then, 500 g of liquid paraffin was added, the temperature was raised to 85° C., and the mixture was stirred at 300 rpm for 2 h. The mixture was allowed to stand for 24 h, and the mixture was centrifuged, washed with petroleum ether, and dried in vacuo to obtain resin microspheres. (6) The resin microspheres are placed in a muffle furnace, and the temperature is raised from room temperature to 800°C at a rate of 3°C / min under a nitrogen atmosphere, and the temperature is kept for 3 h. The microspheres are then cooled to room temperature, washed with water, and vacuum dried to obtain a deodorant.

[0025] Comparative Example 2: The difference between Comparative Example 2 and Example 2 is that: ethylenediamine is not added in step (3); (1) Add 12.6 g of melamine and 9.1 g of stearyl chloride to 100 g of N,N-dimethylformamide, raise the temperature to 80°C, stir and react for 5 h, and rotary evaporate to obtain modified melamine; (2) adding 20 g of modified melamine to 20 g of a 37 wt % formaldehyde aqueous solution, heating to 80° C., and stirring for 30 min to obtain a stearic acid-modified melamine-formaldehyde prepolymer; (3) Add 1 g of silver nitrate to 50 g of deionized water, cool to 0°C, stir for 30 min, then add 20 g of 5 wt% sodium borohydride aqueous solution, stir for 5 min, centrifuge, wash with water, and vacuum dry to obtain silver particles; (4) adding 5 g of melamine and 0.5 g of silver particles into 2.5 g of a 37 wt % formaldehyde aqueous solution, heating to 80° C., and stirring for 30 min to obtain a silver-modified melamine-formaldehyde prepolymer; (5) 40 g of stearic acid-modified melamine-formaldehyde prepolymer, 8 g of silver-modified melamine-formaldehyde prepolymer and 5 g of calcium carbonate were mixed, the temperature was raised to 40°C, and the mixture was stirred for reaction for 1 h. Then, 500 g of liquid paraffin was added, the temperature was raised to 85°C, and the mixture was stirred at 300 rpm for 2 h. The mixture was allowed to stand for 24 h, centrifuged, washed with petroleum ether, and vacuum dried to obtain resin microspheres. (6) The resin microspheres are placed in a muffle furnace, and the temperature is raised from room temperature to 800°C at a rate of 3°C / min under a nitrogen atmosphere, and the temperature is kept for 3 h. The microspheres are then cooled to room temperature, washed with water, and vacuum dried to obtain a deodorant.

[0026] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that: no amide silver particles are added in step (4); (1) Add 12.6 g of melamine and 9.1 g of stearyl chloride to 100 g of N,N-dimethylformamide, raise the temperature to 80°C, stir and react for 5 h, and rotary evaporate to obtain modified melamine; (2) adding 20 g of modified melamine to 20 g of a 37 wt % formaldehyde aqueous solution, heating to 80° C., and stirring for 30 min to obtain a stearic acid-modified melamine-formaldehyde prepolymer; (3) adding 5 g of melamine to 2.5 g of a 37 wt % formaldehyde aqueous solution, heating the solution to 80° C., and stirring the solution for 30 min to obtain a melamine-formaldehyde prepolymer; (4) 40 g of stearic acid-modified melamine-formaldehyde prepolymer, 8 g of melamine-formaldehyde prepolymer and 5 g of calcium carbonate were mixed, the temperature was raised to 40°C, and the mixture was stirred for reaction for 1 h. Then 500 g of liquid paraffin was added, the temperature was raised to 85°C, and the mixture was stirred at 300 rpm for 2 h. The mixture was allowed to stand for 24 h, centrifuged, washed with petroleum ether, and vacuum dried to obtain resin microspheres. (5) The resin microspheres are placed in a muffle furnace, and the temperature is raised from room temperature to 800°C at a rate of 3°C / min under a nitrogen atmosphere, and the temperature is kept for 3 h. The microspheres are then cooled to room temperature, washed with water, and vacuum dried to obtain a deodorant.

[0027] Performance Test: Antibacterial experiment: Staphylococcus aureus (A) and Escherichia coli (B) were cultured in LB medium for 12 hours, and 50 μL of bacterial solution was added to LB agar medium and stirred evenly. After cooling, a round absorbent paper with a diameter of 1.0 cm soaked with the same mass of deodorant prepared in the embodiment and the comparative example was carefully placed in the center of the agar plate, and cultured at 37°C for 6 hours. The size of the antibacterial zone was measured, and the results are shown in Table 1.

[0028] Deodorization experiment: The deodorants prepared in the embodiments and comparative examples were diluted with water at a ratio of 1:500 and evenly sprayed on a plastic bucket containing the same mass of dog feces. A blank control was also performed. The malodorous gas in the plastic bucket was collected using an atmospheric sampler at 0 min, 30 min and 60 min, and the gas was passed into a small impact absorption tube in series with 10 mL of absorption liquid at a flow rate of 0.5 L / min. After absorbing for 5 hours, the contents of hydrogen sulfide and ammonia in the malodorous components were detected by the methylene blue colorimetric method and the titration method, respectively, and the removal rate was calculated. The results are shown in Table 1.

[0029] Table 1 Performance test results

[0030] Data Analysis: From the data of Examples 1-3 and the control group in Table 1, it can be seen that the antibacterial deodorant prepared by the present invention has a good removal effect on hydrogen sulfide and ammonia in the malodorous gas produced by dog ​​feces, which is significantly improved compared with the control group. Moreover, at 30 minutes, the hydrogen sulfide removal rate and the ammonia removal rate can reach more than 50%, indicating that it has a rapid deodorization effect. Moreover, the diameter of the inhibition zone for Staphylococcus aureus (A) and Escherichia coli (B) is significantly higher than that of the control group, indicating that it has a significant antibacterial effect.

[0031] It can be seen from the data of Example 2 and Comparative Example 1 in Table 1 that the use of stearyl chloride to modify melamine can effectively improve the removal effect of the antibacterial deodorant on hydrogen sulfide and ammonia. This is mainly because stearyl chloride occupies the amino sites on melamine and adjusts the crosslinking density with formaldehyde, thereby regulating the pore structure of the antibacterial deodorant, making it easier for hydrogen sulfide and ammonia to diffuse to the adsorption sites in the antibacterial deodorant, thereby improving the removal effect on hydrogen sulfide and ammonia.

[0032] It can be seen from the data of Example 2 and Comparative Example 2 in Table 1 that the amide silver particles prepared by using ethylenediamine can effectively improve the removal effect of the antibacterial deodorant on hydrogen sulfide and ammonia in the malodorous gas produced by dog ​​feces, especially the removal effect of hydrogen sulfide, and improve the antibacterial ability. This is mainly because the amide silver particles can be evenly dispersed in the antibacterial deodorant matrix without blocking the pores and providing more adsorption sites.

[0033] It can be seen from the data of Example 2 and Comparative Example 3 in Table 1 that the addition of silver amide particles can significantly improve the deodorizing effect and antibacterial effect of the antibacterial deodorant.

[0034] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

Claims

1. A method for preparing an antibacterial deodorant, characterized in that: The following steps are involved: (1) Add melamine and stearyl chloride to N,N-dimethylformamide, raise the temperature to 75-85°C, stir and react for 4-6 hours, and rotary evaporate to obtain modified melamine; (2) adding the modified melamine to a 37 wt % formaldehyde aqueous solution, heating the solution to 75-85° C., and stirring for 20-40 min to obtain a stearic acid modified melamine-formaldehyde prepolymer; (3) adding silver nitrate and ethylenediamine to deionized water, cooling to 0-5°C, stirring for 20-40 minutes, then adding a 5wt% sodium borohydride aqueous solution, stirring for 4-6 minutes, centrifuging, washing with water, and vacuum drying to obtain silver amide particles; (4) adding melamine and silver amide particles to a 37 wt % formaldehyde aqueous solution, heating to 75-85° C., and stirring for 20-40 min to obtain a silver-modified melamine-formaldehyde prepolymer; (5) Mixing stearic acid-modified melamine-formaldehyde prepolymer, silver-modified melamine-formaldehyde prepolymer and calcium carbonate, heating to 35-45° C., stirring for reaction for 0.5-1.5 h, adding liquid paraffin, heating to 80-90° C., stirring at a speed of 200-400 rpm for 1.5-2.5 h, standing for 20-28 h, centrifuging, washing, and vacuum drying to obtain resin microspheres; (6) placing the resin microspheres in a muffle furnace, calcining at high temperature under a nitrogen atmosphere, washing with water, and vacuum drying to obtain an antibacterial deodorant; In the step (1), the weight ratio of melamine, stearyl chloride and N,N-dimethylformamide is 10-15:7-11:80-120; In the step (5), the ratio of stearic acid-modified melamine-formaldehyde prepolymer, silver-modified melamine-formaldehyde prepolymer, calcium carbonate and liquid paraffin is 30-50:6-10:3-8:400-600.

2. The method for preparing the antibacterial deodorant according to claim 1, characterized in that: In the step (2), the weight ratio of the modified melamine to the 37 wt % formaldehyde aqueous solution is 15-25:10-30.

3. The method for preparing the antibacterial deodorant according to claim 1, characterized in that: In the step (3), the weight ratio of silver nitrate, ethylenediamine, deionized water and 5 wt% sodium borohydride aqueous solution is 1:0.05-0.5:40-60:15-25.

4. The method for preparing the antibacterial deodorant according to claim 1, characterized in that: In the step (4), the weight ratio of melamine, silver amide particles and 37 wt % formaldehyde aqueous solution is 4-6:0.3-0.8:2-3.

5. The method for preparing the antibacterial deodorant according to claim 1, characterized in that: The high temperature calcination in step (6) is as follows: heating from room temperature to 750-850°C at a rate of 2-4°C / min, keeping the temperature for 2-4h, and cooling to room temperature.

6. An antibacterial deodorant, characterized in that: The antibacterial deodorant is obtained by the preparation method of the antibacterial deodorant according to any one of claims 1 to 5.

Images