CN101836660B - Preparation method of composite nano-antibacterial, as well as antibacterial NL latex and antibacterial TPI rubber - Google Patents

Abstract

The invention discloses a preparation method of composite nano antibacterial agent, antibacterial NL latex and antibacterial TPI rubber. _{Zn ( _ _ _ _ _ _ _ _ _} OH) ₂ and Zn ₅ (OH) ₈ (NO ₃ ) ₂ 2NH ₃ as the core, the precursor of ZnO/Ag composite nano-antibacterial agent coated with Zn ₅ (OH) ₆ (CO ₃ ) ₂ and Ag ₂ CO ₃ . The particle size of the calcined precursor is 10-25nm, and the ZnO/Ag composite nano-antibacterial agent with good antibacterial performance has an MIC lower than 50mg/L. The method has the advantages of simple operation, large output, low cost and easy industrialization. Antibacterial NL latex and antibacterial TPI rubber with good antibacterial properties were prepared by using the obtained antibacterial agent as functional filler.

Description

Preparation method of composite nano antibacterial agent and antibacterial NL latex and antibacterial TPI rubber

technical field

The invention relates to a method for preparing a ZnO/Ag composite nanometer antibacterial agent by a complex precipitation method and using the antibacterial agent as an additive to prepare antibacterial natural (NL) latex and antibacterial TPI rubber.

technical background

Antibacterial agents are divided into three categories: natural, organic and inorganic antibacterial agents. Natural antibacterial agents are mainly natural plant extracts, but their antibacterial effect is not as good as that of organic antibacterial agents, and due to resource constraints, it is difficult to apply and promote them; although organic antibacterial agents are effective quickly and have strong bactericidal ability, they have toxic side effects and are heat-resistant Poor performance, easy to decompose, short service life, and have the defects of secondary pollution. In contrast, inorganic antibacterial agents, especially the rapidly developed nano-inorganic antibacterial agents, nano-inorganic composite antibacterial agents and antibacterial materials made from them have safe, efficient, and broad-spectrum antibacterial properties, which meet the requirements of "green chemistry" "The concept is an environmentally friendly material, so it has attracted much attention.

Among many nano-inorganic antibacterial agents, nano-ZnO is low in cost and non-toxic to human body, which is a promising antibacterial material, but its practical application is limited due to its low antibacterial performance. (Toshiaki Ohira, Osamu Yamamoto, Yasuhiro Iida, Zenbe-e Nakagawa. Antibacterial activity of ZnO powder with crystallographic orientation. JMater Sci: Mater Med, 2008, 19: 1407-1412.). Nano-Ag has high thermal stability and excellent antibacterial durability, but it is easy to change color and the price is high. The compounding of noble metals and metal semiconductor oxides is an effective way to improve their various physical and chemical properties (Young Hwan Kim, Don Keun Lee, Hyun Gil Cha, Chang Woo Kim, Young Soo Kang, Synthesis and Characterization of Antibacterial Ag-SiO ₂ Nanocomposite .J.Phys.Chem.C 2007, 111, 3629-3635.Haibo Zeng, Peisheng Liu, Weiping Cai, Shikuan Yang, Xiaoxia Xu.ControllablePt/ZnO Porous Nanocages with Improved Photocatalytic Activity.J.Phys.Chem.C 2008, 112, 19620-19624. Tsutomu Hirakawa, Prashant V. Kamat. Charge Separation and Catalytic Activity of AgTiO ₂ Core Shell Composite Clusters under UV Irradiation. J AM. CHEM. SOC. 2005, 127(11): 3928-3934). Combining nano-Ag and ZnO, due to the synergistic effect of the two nano-materials, not only overcomes the disadvantage of high cost and easy discoloration of nano-Ag antibacterial agents, but also improves the antibacterial performance of nano-ZnO, thereby obtaining a compound with low cost and high antibacterial activity. Nano antibacterial agent.

At present, there are many methods for preparing composite nanomaterials. For example: the patent of Publication No. CN101550497 invented "the method for preparing nano-silver particle-coated zinc oxide composite material by one-step moist heat method", in addition, the main method of preparing ZnO/Ag composite material reported in the literature also has polymer gel method (Shao Zhongbao , Wang Chengyan, Chen Xuebing, etc. Preparation and photocatalytic properties of nano ZnO/Ag [J]. Journal of Materials Research, 2005, 190 (1): 59-63.), dipping photolysis method (Chen Shihai, NICKEU.Controllable Excition bleaching and recovery observed in ZnO/Ag hybridnanometer-sized particles[J].Chem.Commun., 1996,10(2):133-134.), laser compound heating evaporation technology (Ronghua Wang, Haozhong Xin, Yang Yang, Hongfang Liu, Liming Xu, Junhui Hu. The characteristics and photocatalytic activities of silver doped ZnO nanocrystallites [J]. Applied Surface, Science, 2004, 227: 312-317.), etc., but these methods or processes are complicated, or the preparation conditions are harsh, or High requirements on equipment are not conducive to large-scale production. Therefore, the development of a method for preparing ZnO/Ag composite nano-antibacterial agents with simple operation, controllable products and low cost has important theoretical significance and application value.

Antibacterial NL latex and antibacterial TPI rubber can effectively inhibit the reproduction of harmful microorganisms, so they are widely used in medical materials and other fields. Traditional antibacterial rubber is to mix organic antibacterial additives (tetramine compounds, organic arsenic compounds, etc.) Defects such as toxic and side effects, but also produce unpleasant smells, causing sensory discomfort. (Zheng Xuqi. New antibacterial rubber used in food processing, packaging, medical treatment and other fields. Rubber Reference Materials, 2004, 34(2): 11-14). Therefore, replacing organic antibacterial agents such as organic arsenic compounds with safe, efficient, and broad-spectrum ZnO/Ag composite nano-antibacterial agents will surely endow antibacterial NL latex and antibacterial TPI rubber with more excellent antibacterial properties and broader application prospects. .

Contents of the invention

Aiming at the defects of existing ZnO/Ag composite nano-antibacterial agent and antibacterial NL latex and antibacterial TPI rubber preparation method, the present invention proposes a simple operation and low-cost complex precipitation method to prepare ZnO/Ag composite nano-antibacterial agent and The method for preparing antibacterial NL latex and antibacterial TPI rubber by applying the antibacterial agent.

Specifically, the present invention provides a preparation method for composite nano-antibacterial agent, antibacterial NL latex and antibacterial TPI rubber, which is characterized in that: soluble zinc salt and AgNO ₃ are used as raw materials, and NH ₃ ·H ₂ O is used as a complexing agent to prepare complex solution. After the complex is hydrolyzed to form a partial precipitate, the precipitating agent is added dropwise at a rate of 2-15ml/s, and after the precipitation is complete, it is centrifuged, washed, and dried to obtain the precursor of the ZnO/Ag composite nano-antibacterial agent. The precursor is calcined to obtain a ZnO/Ag composite nanometer antibacterial agent with a particle size of 10-25nm and good antibacterial properties. Antibacterial NL latex and antibacterial TPI rubber were prepared by impregnation method and double-roll mixing method with the obtained ZnO/Ag composite nano-antibacterial agent as additive.

In the above method, the preparation method of the composite nano antibacterial agent is characterized in that: the raw material soluble zinc salt can be Zn(NO ₃ ) ₂ or Zn(Ac) ₂ with a concentration of 1mol/L; the complexing agent is NH ₃ H ₂ O , wherein the mass percentage of NH ₃ is 25% to 28%, and the precipitation agent can be (NH ₄ ) ₂ CO ₃ or Na ₂ CO ₃ or a mixture of (NH ₄ ) ₂ CO ₃ and Na ₂ CO ₃ . The ratio of the amount of raw materials, complexing agent and precipitating agent is n(soluble zinc salt):n(AgNO ₃ ):n(NH ₃ ·H ₂ O):n(precipitating agent)=1:0.02～0.33: 4.10~4.70: 1.52~1.75.

In the above method, the synthesis temperature of the precursor of the ZnO/Ag composite nano antibacterial agent is 50-70° C., the reaction time of one step is 35-55 minutes, and the reaction time of two steps is 120-150 minutes.

In the above method, the precursor of the ZnO/Ag composite nano-antibacterial agent is to use Zn(OH) ₂ and Zn ₅ (OH) ₈ (NO ₃ ) ₂ · 2NH ₃ as the core, Zn ₅ (OH) ₆ (CO ₃ ) ₂ and Ag ₂ CO ₃ as the outer cladding layer.

In the above method, calcining the precursor of the ZnO/Ag composite nano-antibacterial agent is carried out in two steps in an ordinary box-type resistance furnace or a vacuum atmosphere furnace. Zn(OH) ₂ and Zn ₅ (OH) ₈ (NO ₃ ) ₂ ·2NH ₃ in the core decompose first, and then crack Zn ₅ (OH) ₆ (CO ₃ ) ₂ and Ag ₂ CO ₃ in the outer cladding , which is beneficial to obtain small-sized products. Then raise the temperature to 350-450°C and keep it warm for 240 minutes to completely decompose Zn ₅ (OH) ₆ (CO ₃ ) ₂ and Ag ₂ CO ₃ . After cooling in the furnace, a ZnO/Ag composite nano-antibacterial agent with a particle size of 10-25nm and good antibacterial properties can be obtained. The present invention also provides a preparation method of antibacterial NL latex, which is characterized in that: under the premise of substantially not changing the conventional process and formula of NL latex prepared by dipping method, the dispersed ZnO/ Antibacterial NL latex was prepared by Ag composite nano antibacterial agent.

The preparation process of antibacterial NL latex is as follows: firstly carry out latex compounding, under mechanical stirring, add casein solution, KOH solution, accelerator dispersion and vulcanizing agent dispersion to the latex in turn, then add ZnO/Ag composite nano antibacterial agent, Precure in a constant temperature water bath at 60-70°C for 30 minutes, cool to room temperature, then add accelerator dispersion, vulcanizing agent dispersion, anti-aging agent dispersion, and lanolin emulsion in sequence to obtain latex, and filter for use. Then prepare the latex sheet, put the model in the starch coagulant for 30s, put it out, dry it in hot air at 80°C, immerse it in the pre-vulcanized latex, put it out after staying for 30s, and dry it at 70°C for 1-1.5h to obtain Antibacterial latex.

The present invention also provides a preparation method of antibacterial TPI rubber, which is characterized in that: under the premise of basically not changing the conventional process and formula of TPI rubber prepared by double-roll mixing method, in the mixing stage, the dispersed ZnO/Ag composite nano The antibacterial agent is added into the rubber at a ratio of 0.74-6.27% to make antibacterial TPI rubber.

The preparation process of antibacterial TPI rubber is as follows: first, heat up the mill to 50-70°C, add rubber compound, masticate for 3-7 minutes, until the rubber compound is covered with rolls. Then carry out mixing, and in the mixing process, first add stearic acid, anti-aging agent, accelerator, reinforcing agent in sequence, then add composite nano antibacterial agent, and finally add sulfur. Continue mixing for 20-30 minutes. After the overall color of the rubber is uniform, adjust the roller distance to about 1mm, pack the triangle bag six times, and vulcanize at 143-150°C and 15MPa pressure for 27-32 minutes to prepare antibacterial TIP rubber.

The technical scheme of the present invention is: adopt complex precipitation method to prepare ZnO/Ag composite nano-antibacterial agent, and use the antibacterial agent as additive, adopt dipping method to prepare antibacterial NL latex, adopt double-roller mixing method to prepare antibacterial TPI rubber. It is characterized by:

(1) Using soluble zinc salt [Zn(NO ₃ ) ₂ or Zn(Ac) ₂ ] and AgNO ₃ as raw materials, and NH ₃ ·H ₂ O as a complexing agent, react to form a complex solution. The amount ratio of soluble zinc salt, AgNO ₃ and NH ₃ ·H ₂ O is n(soluble zinc salt):n(AgNO ₃ ):n(NH ₃ ·H ₂ O)=1:0.02～0.33: 4.10~4.70.

(2) At 50-70°C, first carry out the hydrolysis reaction for 35-55 minutes, after forming part of the precipitate, then press soluble zinc salt, AgNO ₃ , NH ₃ ·H ₂ O and precipitant [(NH ₄ ) ₂ CO ₃ or Na ₂ CO ₃ or a mixture of (NH ₄ ) ₂ CO ₃ and Na ₂ CO ₃ ] the ratio of the amount of substances is n(soluble zinc salt):n(AgNO ₃ ):n(NH ₃ ·H ₂ O): n (precipitant)=1: 0.02～0.33: 4.10～4.70: 1.52～1.75, drop the precipitant at a speed of 2～15ml/s, and continue the reaction for 120～150min.

_{( 3} ) _{Centrifuge after stopping the} reaction, _wash and dry to obtain Zn ₅ (OH) ₆ (CO ₃ ) ₂ And Ag ₂ CO ₃ is the precursor of the outer cladding layer.

(4) Put the container containing the body in the furnace, first raise the furnace temperature to 200°C, keep it warm for 60-120min, then raise the temperature to 350-450°C, keep it warm for 240min, and cool with the furnace, you can get a particle size of about 10-25nm, ZnO/Ag composite nano-antibacterial agent with good antibacterial properties.

(5) Under the premise of basically not changing the conventional process and formula of NL latex prepared by dipping method, the antibacterial NL latex was prepared by adding the dispersed ZnO/Ag composite nano-antibacterial agent in a proportion of 0.29-0.67%. The preparation process is as follows: First, under mechanical stirring, add casein solution, KOH solution, accelerator dispersion, and vulcanizing agent dispersion to the latex in sequence, then add the dispersed ZnO/Ag composite nano-antibacterial agent, at 60-70 ° C Pre-sulfurize in a constant temperature water bath for 30 minutes, cool to room temperature, and then add accelerator dispersion, vulcanizing agent dispersion, anti-aging agent dispersion, and lanolin emulsion in sequence to obtain latex, and filter for later use. Then the model was dipped in starch coagulant for 30s and raised, dried in hot air at 80°C, immersed in pre-vulcanized latex, held for 30s, lifted out, dried at 70°C for 1-1.5h, and antibacterial latex was obtained.

(6) Under the premise of basically not changing the conventional process and formula of TPI rubber prepared by double-roller mixing method, the dispersed ZnO/Ag composite nano-antibacterial agent was added to the rubber to make antibacterial TPI rubber.

The preparation process is as follows: first, the temperature of the open mill is raised to 50-70° C., and rubber compound is added, and masticated for 3-7 minutes until the rubber compound is covered with rolls. Then carry out mixing, and in the mixing process, first add stearic acid, anti-aging agent, accelerator, reinforcing agent in sequence, then add composite nano antibacterial agent, and finally add sulfur. Continue mixing for 20-30 minutes. After the overall color of the rubber is uniform, adjust the roller distance to about 1mm, pack the triangle bag six times, and vulcanize at 143-150°C and 15MPa pressure for 27-32 minutes to prepare antibacterial TIP rubber.

Description of drawings

The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

Figure 1 is a process flow chart for preparing ZnO/Ag composite nano-antibacterial agent, antibacterial NL latex and antibacterial TPI rubber by complex precipitation method.

Fig. 2 is the X-Ray diffraction spectrum of the ZnO/Ag composite nano antibacterial agent obtained in Example 1.

Fig. 3 is the transmission electron micrograph of the ZnO/Ag composite nano antibacterial agent obtained in Example 1.

Fig. 4 is the photo of the antibacterial experiment of the ZnO/Ag composite nano antibacterial agent obtained in Example 1 against Escherichia coli. Wherein the picture (a) has no antibacterial agent; (b) antibacterial agent concentration is 20mg/L; (c) antibacterial agent concentration is 50mg/L.

Figure 5 is the X-Ray diffraction pattern of the ZnO/Ag composite nano antibacterial agent obtained in Example 2.

Figure 6 is a transmission electron micrograph of the ZnO/Ag composite nano-antibacterial agent obtained in Example 2.

Fig. 7 is the photo of the antibacterial experiment of the ZnO/Ag composite nano antibacterial agent obtained in Example 2 against Escherichia coli bacteria. Wherein (a) no antibacterial agent; (b) antibacterial agent concentration is 20mg/L; (c) antibacterial agent concentration is 40mg/L.

Fig. 8 is an antibacterial experiment photo of antibacterial NL latex to Staphylococcus aureus. Wherein (a) no antibacterial agent; (b) 0.1g antibacterial agent; (c) 0.5g antibacterial agent.

Figure 9 is a photo of the antibacterial experiment of antibacterial TPI rubber against Escherichia coli bacteria. Wherein (a) no antibacterial agent; (b) 1g antibacterial agent; (c) 5g antibacterial agent.

Detailed ways

The process flow of preparing ZnO/Ag composite nano-antibacterial agent, antibacterial NL latex and antibacterial TPI rubber is shown in Figure 1.

Example 1. Using Zn(NO ₃ ) ₂ and AgNO ₃ as raw materials, NH ₃ ·H ₂ O as a complexing agent, (NH ₄ ) ₂ CO ₃ as a precipitating agent, and using complex precipitation to prepare ZnO/Ag composite nano Antibacterial agents.

(1) Take 30ml of Zn(NO ₃ ) ₂ solution with a concentration of 1mol/L in a three-necked flask, add 10ml of concentrated NH ₃ H ₂ O with a mass percentage of 25% to 28% under stirring, and then press the raw material The ratio of the amount of substances is n[Zn(NO ₃ ) ₂ ]:n[AgNO ₃ ]=1:0.083 Add 15ml of AgNO ₃ solution with a concentration of 0.168mol/L to fully react to obtain a clear and transparent complex solution.

(2) After the complex solution was hydrolyzed at 60°C for 45min, 45ml of (NH ₄ ) ₂ CO ₃ solution with a concentration of 1mol/L was added dropwise at a rate of 3ml/s, and the reaction was continued at the same temperature for 120min before stopping . Centrifuge, wash with distilled water and ethanol, and dry the precipitate in a drying oven to obtain Zn(OH) ₂ and Zn ₅ (OH) ₈ (NO ₃ ) ₂ · ₂ NH ₃ cores, coated with Zn ₅ (OH) ₆ (CO ₃ ) ₂ and Ag ₂ CO ₃ are the precursors of the ZnO/Ag composite nano-antibacterial agent.

(3) Put the crucible containing the precursor in the furnace, first raise the furnace temperature to 200°C, keep it for 90 minutes, then continue to heat up to 350°C, keep it for 240 minutes, and then cool with the furnace to get ZnO with hexagonal wurtzite structure. The ZnO/Ag composite nano-antibacterial agent of the Ag of crystal and cubic structure, its X-Ray diffraction pattern is shown in Fig. 2; The photo of the antibacterial experiment of Escherichia coli is shown in Figure 4. The minimum inhibitory concentration of the antibacterial agent is 50mg/L, which is better than the standard stipulated in HG/T 3794-2005 "Inorganic Antibacterial Agents - Performance and Evaluation".

Example 2. The operation steps are the same as in Example 1, but the precipitating agent is Na ₂ CO ₃ , and the raw material ratio is controlled n[Zn(NO ₃ ) ₂ )]:n[AgNO ₃ ]:n[NH ₃ ·H ₂ O]: n[Na ₂ CO ₃ ] is 1:0.09:4.31:1.67, the reaction time of one step is 55min, and the reaction time of two steps is 150min. When calcining the precursor, first keep it at 200°C for 120min, then continue to heat up to 450°C and hold it for 240min. With furnace cooling, the obtained antibacterial agent is the same as Example 1, which is a composite of hexagonal wurtzite structure ZnO crystal and cubic structure Ag, and its X-Ray diffraction pattern is shown in Fig. 5; See Figure 6 for the photo; see Figure 7 for the antibacterial experiment photos of the antibacterial agent against Escherichia coli with different dosages. The minimum inhibitory concentration of the antibacterial agent is 40mg/L, which is better than the standard stipulated in HG/T 3794-2005 "Inorganic Antibacterial Agents - Performance and Evaluation".

Example 3. Preparation of antibacterial NL latex.

Under mechanical stirring, add 5g 10% casein solution, 1g 10% KOH solution, 2g 50% accelerator TMTD dispersion, 0.6g 50% S dispersion, 1g 50% ZnO/Ag composite to 100g natural rubber latex successively Nano antibacterial agent dispersion, pre-vulcanized in a constant temperature water bath at 70°C for 30 minutes, then cooled to room temperature, then added 1g of 50% accelerator ZDC dispersion, 0.4g of 50% S dispersion, and 1g of 50% anti-aging agent 264 dispersion , 2.5g of 20% lanolin emulsion to obtain latex, filtered for later use. The model was dipped in starch coagulant for 30s, dried in hot air at 80°C, then immersed in pre-vulcanized latex, lifted for 30s, and dried at 70°C for 1 hour to obtain antibacterial NL latex. The antibacterial experiment photos of the antibacterial NL latex prepared by adding different amounts of antibacterial agents against Staphylococcus aureus are shown in Figure 8. When the amount of antibacterial agent is 0.5g, the antibacterial rate is 99.62%, which is better than the 2002 disinfection technical standard.

Embodiment 4. Preparation of antibacterial TPI rubber.

First, raise the temperature of the mill to 70°C, add 100g TPI, and masticate for 5 minutes. After the rubber material is covered with rolls, add 1g (C ₁₇ H ₃₅ COO) ₂ AlOH, 3g C ₁₈ H ₂₂ O ₂ , 30g CaCO ₃ and 5g of dispersed ZnO/Ag composite nano-antibacterial agent, and finally add 0.5g of S. After mixing evenly, adjust the roller distance to about 1mm, pack the triangular bag six times, and vulcanize for 30min at 45°C and 15MPa to prepare antibacterial TPI rubber. The antibacterial experiment photos of the antibacterial TPI rubber prepared by adding different amounts of antibacterial agents against Escherichia coli are shown in Figure 9. When the amount of antibacterial agent is 5g, the antibacterial rate is 99.67%, which is better than the 2002 disinfection technical standard.

Claims (5)

1. the preparation method of antibiotic NL latex and antibiotic TPI rubber is characterized in that: with soluble zinc salt and AgNO ₃Be raw material, NH ₃H ₂O is a complexant, makes complex solution, make complex hydrolysis generate partly precipitated after; Speed with 2～15ml/s drips precipitating reagent again, treats deposition fully, centrifugation, washing, drying; Get the precursor of ZnO/Ag composite nano antibacterial agent; It is 10～25nm that the calcining precursor obtains particle diameter, has the ZnO/Ag composite nano antibacterial agent of good anti-microbial property, is additive with gained ZnO/Ag composite nano antibacterial agent; Adopt infusion process and twin-roll mixing method to make antibiotic NL latex and antibiotic TPI rubber respectively

In the preparation method of antibiotic NL latex, under the prerequisite that does not change immersion process for preparing NL latex common process and prescription basically, the ZnO/Ag composite nano antibacterial agent after latex cooperates the stage in 0.29～0.67% ratio adding dispersion makes antibiotic NL latex,

Antibiotic NL latex preparation technology is following: at first carry out latex and cooperate, under mechanical agitation, in latex, add casein solution, KOH solution successively; The promoter dispersion after the vulcanizing agent dispersion, adds the ZnO/Ag composite nano antibacterial agent again, presulfurization 30min in 60～70 ℃ of waters bath with thermostatic control; Be cooled to room temperature, and then add the promoter dispersion successively, vulcanizing agent dispersion, age resistor dispersion; Lanolin emulsion makes latex, filters for use; Carry out photoplate preparation then, propose model flood 30s in the starch coagulating agent after, in the latex that the immersion presulfurization of dry back is good in 80 ℃ of hot-airs; Propose after stopping 30s,, make antibiotic NL latex in 70 ℃ of drying 1～1.5h;

In the preparation method of antibiotic TPI rubber; Not changing basically under the prerequisite that the twin-roll mixing legal system is equipped with TPI rubber common process and prescription,, the ZnO/Ag composite nano antibacterial agent after disperseing is joined in the rubber in 0.74～6.27% ratio in mix stage; Process antibiotic TPI rubber

Antibiotic TPI rubber preparation technology is following: earlier mill is warming up to 50～70 ℃, adds rubber size, 3～7min plasticates; To sizing material bag roller, carry out subsequently mixing, and in mixing process; Add stearic acid, age resistor, promoter, reinforcing agent at first successively, and then add composite nano antibacterial agent, add sulphur at last; Continued mixing 20～30 minutes, treat that the rubber integral color evenly after, roll spacing is transferred to about 1mm; Play the triangle bag six times, under 143～150 ℃ and 15MPa pressure, sulfuration 27～32min prepares antibiotic TIP rubber.

2. preparation method according to claim 1 is characterized in that: the raw material soluble zinc salt can be Zn (NO ₃) ₂Or Zn (Ac) ₂, concentration is 1mol/L; Complexant is NH ₃H ₂O, wherein NH ₃The quality percentage composition be 25%～28%, precipitating reagent can be (NH ₄) ₂CO ₃Or Na ₂CO ₃Or (NH ₄) ₂CO ₃And Na ₂CO ₃Both mixtures, the ratio of the amount of substance of raw material, complexant and precipitating reagent is soluble zinc salt: AgNO ₃: NH ₃H ₂O: precipitating reagent=1: 0.02～0.33: 4.10～4.70: 1.52～1.75.

3. the preparation method of composite nano antibacterial agent according to claim 1, it is characterized in that: the synthesis temperature of the precursor of ZnO/Ag composite nano antibacterial agent is 50～70 ℃, and the single step reaction time is 35～55min, and two reaction time in step were 120～150min.

4. the preparation method of composite nano antibacterial agent according to claim 1 is characterized in that: the precursor of ZnO/Ag composite nano antibacterial agent is for Zn (OH) ₂And Zn ₅(OH) ₈(NO ₃) ₂2NH ₃Be nuclear, Zn ₅(OH) ₆(CO ₃) ₂And Ag ₂CO ₃Be external coating.

5. the preparation method of composite nano antibacterial agent according to claim 1; It is characterized in that: the precursor of calcining ZnO/Ag composite nano antibacterial agent carries out in common chamber type electric resistance furnace or vacuum atmosphere oven in two steps; Earlier at 200 ℃ of insulation 60～120min down, make decomposition temperature lower and be positioned at the Zn (OH) of precursor heart portion ₂And Zn ₅(OH) ₈(NO ₃) ₂2NH ₃Decompose earlier, and with the Zn of external coating ₅(OH) ₆(CO ₃) ₂And Ag ₂CO ₃Burst apart, help obtaining the small size product, and then be warming up to 350～450 ℃, and insulation 240min, make Zn ₅(OH) ₆(CO ₃) ₂And Ag ₂CO ₃Decompose fully, with the stove cooling, get particle diameter 10～25nm, tool is with the ZnO/Ag composite nano antibacterial agent of good anti-microbial property.

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