Preparation and application of superfine sodium zirconium phosphate and its loaded antibacterial agent

Abstract

The application relates to the technical field of antibacterial agents, and provides a preparation and application of superfine cubic sodium zirconium phosphate and a loaded antibacterial agent, which solve the defect of large particle size of zirconium phosphate obtained by an existing preparation method and comprises the following preparation steps: (1) a zirconium-containing compound and a phosphate-containing compound are weighed, a crystal form inducer is added, and then a mixed and uniform composite powder is formed by grinding for more than 30 min; (2) a sodium nitrate and ammonium oxalate-containing aqueous solution is prepared; (3) the prepared composite powder in the first step is weighed according to a proportion, the composite powder is slowly added into the aqueous solution prepared in the step (2) under continuous stirring, and after all the composite powder is added, continuous stirring is carried out and the solution is kept boiling for 2-3 hours; (4) after the reaction is completed, the solution is cooled to room temperature, the pH value is adjusted to weak acidity, and a cationic organic flocculating agent is added, so that cubic sodium zirconium phosphate precipitates are obtained; after dehydration, cleaning and drying, cubic sodium zirconium phosphate powder is obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of antibacterial agents, and particularly relates to preparation and application of superfine cubic sodium zirconium phosphate and a loaded antibacterial agent thereof. BACKGROUND

[0002] Inorganic antibacterial agents refer to mainly utilizing the antibacterial ability of silver, copper, zinc and other metals or metal ions, and fixing the metal ions on the surface or channel of porous materials such as zeolite, silica gel, titanium oxide and zirconium phosphate through physical adsorption or ion exchange, and then adding them into products to obtain materials with antibacterial properties. Inorganic antibacterial agents have high stability and safety, and are widely used in the fields of ceramics, glass, plastics and fibers. The most significant advantage of using sodium zirconium phosphate as a carrier for loading silver ions is that it will not cause the plastic to discolor when mixed into the plastic, which is an advantage that other inorganic carriers cannot match. Japan was the first to discover this advantage of zirconium phosphate carrier, and began to use it on a large scale to load silver ions to prepare antibacterial agents.

[0003] Sodium zirconium phosphate is often used as a carrier for silver ions, zinc ions and copper ions due to its large specific surface area and surface charge density, and is used to prepare antibacterial agents such as silver phosphate, zinc phosphate and copper phosphate. In sodium zirconium phosphate powder, the pores provide sufficient conditions for the contact between metal ions and bacteria, thereby achieving good bactericidal effect with less antibacterial agent. When the same mass is used, the smaller the particle size of the antibacterial powder, the larger the specific surface area. If it is added to a polymer to prepare antibacterial products such as antibacterial fabrics, antibacterial pads and antibacterial insoles, it will exhibit better antibacterial effect.

[0004] However, the particle size of sodium zirconium phosphate prepared by traditional methods is usually large. For example, the sodium zirconium phosphate powder prepared in Chinese patent application CN111498824A has a D50 range of 10-100 μm; the average particle size of the sodium zirconium phosphate prepared in Chinese patent application CN105401244A is 1-3 μm; and the particle size distribution of the sodium zirconium phosphate powder prepared in Chinese patent application CN102180455A is concentrated in the range of 1-10 μm. The particle size of the carrier measured by a laser particle size analyzer in Chinese patent application CN102763678A is D50 ≤ 1.0 μm and D90 ≤ 2.0 μm. The particle size of the silver-loaded antibacterial powder is D50 ≤ 1.5 μm and D90 ≤ 2.5 μm. The particle size D90 of most products sold on the domestic market is also above 2 μm.

[0005] Chinese patent application No. 201110134080.6 discloses a method for preparing sodium zirconium phosphate powder, comprising the following steps: (1) preparing a 0.06-0.12 mol / l zirconium oxychloride ZrOCl2 solution, and adding sodium polyphosphate to the solution, with the mass ratio of sodium polyphosphate to zirconium oxychloride ZrOCl2 controlled at 2:5-4:5; (2) mixing the sodium polyphosphate, zirconium oxychloride ZrOCl2 and water according to the formula, and then adding them into a high-pressure reaction kettle, with the filling degree of the reaction kettle controlled at 60%-80%, and the temperature controlled at 140-200°C under stirring, and keeping the heat balance at the temperature for 5 hours or more, until the reaction is completed, and then cooling to room temperature; (3) filtering, washing and low-temperature drying the synthesized product to obtain sodium zirconium phosphate powder. The sodium zirconium phosphate powder obtained by the method has a particle size of 1-10 μm. By using this method, the zirconium oxychloride is gradually dispersed in the sodium polyphosphate solution at the initial stage of addition, and the zirconium ion concentration is very high in the region close to the zirconium oxychloride, and very low in other regions, with a large difference in the molar ratio of zirconium ions and phosphate ions in different regions. The reaction speed of zirconium ions and phosphate ions is relatively fast, and thus problems such as different particle sizes and large particle size of the particles may occur.

[0006] Therefore, there are still technical bottlenecks in the industrial production of nanoscale sodium zirconium phosphate and antibacterial agents using nanoscale sodium zirconium phosphate as a carrier. SUMMARY

[0007] Therefore, in view of the above problems, the present application provides a preparation method and application of ultrafine cubic sodium zirconium phosphate and loaded antibacterial agents, which solves the problem of large particle size of sodium zirconium phosphate obtained by the existing preparation method.

[0008] To achieve the above-mentioned purpose, the present application adopts the following technical solution: a preparation method of ultrafine cubic sodium zirconium phosphate, comprising the following preparation steps:

[0009] (1) weighing a zirconium-containing compound and a phosphate-containing compound according to a molar ratio of zirconium ions to phosphate ions of 1-2:3-4, adding 10-50 ppm of a crystal form inducer, and then grinding by a grinder for 30 minutes or more to form a uniformly mixed composite powder;

[0010] (2) preparing an aqueous solution containing 0.2-0.3 mol / L sodium nitrate and 0.2-0.3 mol / L ammonium oxalate;

[0011] (3) weighing the composite powder prepared in the first step according to a molar concentration ratio of zirconium ions to sodium ions in the final solution of 1-1.5, and slowly adding the composite powder into the aqueous solution prepared in step (2) under continuous stirring, and continuously stirring and keeping the solution boiling for 2-3 hours after all the composite powder is added;

[0012] (4) after the reaction is completed, cooling to room temperature, adjusting the pH value to weak acidity with an acid regulator, and adding 5-15 ppm of a cationic organic flocculant to obtain cubic zirconium phosphate sodium precipitate; after dehydration, washing, and drying, cubic zirconium phosphate sodium powder is obtained;

[0013] The zirconium-containing compound refers to zirconium carbonate or zirconium oxychloride; the phosphate-containing compound is diammonium hydrogen phosphate or ammonium dihydrogen phosphate.

[0014] Further, the particle size distribution of the cubic zirconium phosphate sodium powder is less than 500 nm in the 95% area.

[0015] Further, the acid regulator is nitric acid.

[0016] Further, the crystal form inducer refers to cubic zirconium phosphate sodium powder with a particle size of less than 30 nm.

[0017] Further, in step (3), the fluorine ions are added after all the composite powders are added, and the amount of the fluorine ions is 0.01-0.05 wt% of the weight of the composite powders.

[0018] A preparation method of the above-mentioned superfine cubic zirconium phosphate sodium carrier antibacterial agent, comprising the following preparation steps:

[0019] Step one: the cubic zirconium phosphate sodium powder prepared above is mixed with deionized water, the pH value of the solution is adjusted to 2-3 with nitric acid, and continuous stirring is performed to form a milky white solution; the mass fraction of the cubic zirconium phosphate sodium powder in the milky white solution is 18-22 wt%;

[0020] Step two: silver is used as the anode and the cathode, the milky white solution prepared in step one is inserted, square wave direct current is introduced for electrolysis to generate silver ions; the silver ions exchange with sodium ions in the cubic zirconium phosphate sodium crystal to prepare a cubic zirconium phosphate silver antibacterial agent; after dehydration, washing, and drying, a superfine cubic zirconium phosphate silver antibacterial powder product is obtained;

[0021] or, zinc is used as the anode and the cathode, the milky white solution prepared in step one is inserted, square wave direct current is introduced for electrolysis to generate zinc ions; the zinc ions exchange with sodium ions in the cubic zirconium phosphate sodium crystal to prepare a cubic zirconium phosphate zinc antibacterial agent; after dehydration, washing, and drying, a superfine cubic zirconium phosphate zinc antibacterial powder product is obtained;

[0022] or, copper is used as the anode and the cathode, the milky white solution prepared in step one is inserted, square wave direct current is introduced for electrolysis to generate copper ions; the copper ions exchange with sodium ions in the cubic zirconium phosphate sodium crystal to prepare a cubic zirconium phosphate copper antibacterial agent; after filtration, washing, and drying, a superfine cubic zirconium phosphate copper antibacterial powder product is obtained;

[0023] Or, respectively, silver and zinc are used as two poles, respectively, and are inserted into the milky white solution prepared in step one, a square wave direct current is introduced to generate silver ions and zinc ions by electrolysis; the silver ions and zinc ions exchange with sodium ions in the sodium zirconium phosphate crystal to prepare a zirconium phosphate silver zinc antibacterial agent, which is dehydrated, washed and dried to obtain an ultra-fine cubic zirconium phosphate silver zinc antibacterial powder product.

[0024] The square wave direct current refers to the current direction of the cathode and the anode changes according to a certain period, that is, the cathode becomes the anode and the anode becomes the cathode; the current direction transformation period of the square wave direct current is 1-5 min / time; the density of the direct current is 0.05-0.5 A / cm 2 ;

[0025] In the cubic zirconium phosphate silver, cubic zirconium phosphate zinc, cubic zirconium phosphate copper, and cubic zirconium phosphate silver zinc antibacterial agent, silver, zinc and copper elements exist in the form of metal ions.

[0026] An antibacterial product, the product contains 0.05-30wt% of the above-mentioned antibacterial agent, the product is any one of antibacterial masterbatch, toys, ceramic and bathroom products, medical equipment, film, pipe, profile, 3D printing products, sheet, coating, belt, strip, molded part, pipeline, foam, tape, fabric, wire, filament, ribbon, fiber, fiber web, sealant, automotive interior, impregnated product, sheet molding product, hot melt adhesive, adhesive layer, film, insole, yoga mat, floor mat, training mat.

[0027] Further: the product also contains 0.1-1wt% of an organic antibacterial agent.

[0028] Further: the organic antibacterial agent is at least one of organic metal antibacterial agent, organic halide antibacterial agent, alcohol, phenol, ether, aldehyde, ketone, quinone, acid, salt, ester, nitrile, guanidine, organic nitro compound, organic phosphorus, organic arsenic, furan, pyrrole, imidazole, benzofuran, benzothiazole, heterocyclic antibacterial agent.

[0029] By adopting the foregoing technical solutions, the application has the following beneficial effects:

[0030] 1. The product has a small particle size. The particle size distribution D90 of the zirconium phosphate sodium powder prepared by the scheme is within 500 nm, which is much smaller than that of the prior art.

[0031] 2. Environmental protection. Electrolysis is used to obtain silver ions, zinc ions and copper ions, instead of using metal salts as ion sources, which can reduce the content of acid ions in wastewater. The electrolyte can be recycled, achieving zero discharge.

[0032] 3. Short reaction cycle. The reaction time of traditional preparation of zirconium phosphate is generally more than 20 hours, while the production cycle of the present application can be shortened to less than 4 hours, greatly improving the production efficiency.

[0033] 4. In the preparation process of the cubic sodium zirconium phosphate powder, fluorine ions are added to complex with the zirconium ions contained in the composite powder, enhance the activity of the zirconium component, and reduce the reaction temperature. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 is the XRD pattern of commercially available sodium zirconium phosphate powder and the sodium zirconium phosphate and silver zirconium phosphate, zinc zirconium phosphate samples of the present application examples 1-4;

[0035] Figure 2 is the SEM pattern of the sodium zirconium phosphate of the present application example 1;

[0036] Figure 3 is the antibacterial effect diagram of the antibacterial agent prepared by the present application examples 3-6. DETAILED DESCRIPTION

[0037] The present application uses zirconium oxide or zirconium oxychloride as the zirconium source and diammonium hydrogen phosphate or phosphoric acid as the phosphorus source.

[0038] First, the zirconium source and the phosphorus source are ground to prepare a composite powder or slurry with a molar ratio of zirconium ions to phosphate ions of 2:3. The grinding is carried out in an inert atmosphere of nitrogen or helium. The role of this grinding is to mix the zirconium source and the phosphorus source thoroughly, so that the concentration ratio of zirconium ions to phosphate ions is 2:3 in the subsequent operation. This important detail control is ignored in the prior art, which usually adds one substance or its solution to another substance. For example, zirconium oxychloride solution is directly added to sodium phosphate solution. In this operation, at the initial stage, zirconium oxychloride gradually spreads in the sodium phosphate solution, the zirconium ion concentration is very high near the added zirconium oxychloride, and the zirconium ion concentration is very low in other areas, the molar ratio of zirconium ions to phosphate ions in different areas is very different. The reaction rate of zirconium ions and phosphate ions is relatively fast, so there are problems of different particle sizes and large particle size. In the present application, the zirconium-containing compound, the phosphate-containing compound and the crystal type inducer are mixed uniformly by grinding to ensure that the ratio of zirconium ions, phosphate ions and crystal type inducer is relatively fixed at any time, and the nano-powder with specific morphology structure is easily obtained.

[0039] Second, a water solution containing 0.2-0.3 mol / L of sodium nitrate and 0.2-0.3 mol / L of ammonium oxalate is prepared.

[0040] Third step, according to the ratio of the molar concentration of zirconium ions and sodium ions in the final solution is 1-2, slowly add the composite powder or slurry prepared in the first step to the aqueous solution prepared in the second step under continuous stirring, after all the composite powder or slurry is added, continue to stir and keep the solution boiling for 2-3 hours.

[0041] Fourth step, cool the solution after reaction, adjust the pH value to weak acidity with nitric acid, and add 5-15 ppm of cationic organic flocculants to obtain cubic zirconium sodium phosphate precipitate; after filtering, washing and drying, cubic zirconium sodium phosphate powder is obtained. Using nitric acid acidification, impurity metal ions in the solution can be dissolved in the solution instead of being precipitated together with cubic zirconium sodium phosphate in the form of precipitate, so as to prepare high-purity cubic zirconium sodium phosphate powder.

[0042] Further, load silver ions, zinc ions and copper ions on the prepared cubic zirconium sodium phosphate powder to prepare inorganic antibacterial agent, the process is as follows: dissolve the prepared cubic zirconium sodium phosphate powder in deionized water, according to weight parts, 1 part of cubic zirconium sodium phosphate powder corresponds to 2-3 parts of water; stir to make the cubic zirconium sodium phosphate powder suspended in the aqueous solution to form a milky white solution; adjust the pH value of the solution to 2-3 with nitric acid; then use silver, zinc or copper as electrolyte, and produce silver ions, zinc ions or copper ions by electrolysis of square wave direct current. The addition of nitric acid forms an acidic environment, and silver ions, zinc ions and copper ions are not easy to hydrolyze and precipitate, which is conducive to ion exchange with sodium ions in cubic zirconium sodium phosphate; the advantage of square wave current is conducive to removing the scale on the surface of the electrode, because the anode surface is easy to scale during electrolysis, and the cathode is not easy to scale, by changing the polarity of the electrode through square wave current, the problem of scale on the surface of the electrode can be effectively and automatically cleaned. The frequency of square wave current has no effect on the quality and physical properties of the antibacterial agent product, only the electrode life and electrode scaling problem are affected, the faster the frequency changes, the shorter the electrode life, the slower the frequency changes, the more likely the electrode is to scale. The smaller the current density, the more uniform the amount of silver ions loaded on each cubic zirconium sodium phosphate particle in theory, but the smaller the current density, the longer the production cycle. Therefore, considering the industrial production efficiency and cost, the current direction changing period of square wave current is 3-5 min / time, and the density of direct current is 0.05-0.5 A / cm 2 It is relatively optimal.

[0043] Furthermore, based on antibacterial performance requirements and product characteristics, the prepared antibacterial agent can be added to polymeric or inorganic materials to prepare various products with antibacterial functions. Typically, for polymeric products, the agent can be added through melt blending; for inorganic products, such as ceramic products, it can be added during raw material preparation, ensuring thorough mixing of the antibacterial agent with the ceramic raw materials before further processing and sintering. The antibacterial agent prepared using this technical solution can be used to prepare toys, ceramic sanitary ware products, medical devices, films, pipes, profiles, 3D printed products, sheets, coatings, belts, strips, molded parts, pipes, foams, tapes, fabrics, threads, filaments, ribbons, fibers, fiber webs, sealants, automotive interiors, impregnated products, sheet molded products, hot melt adhesives, adhesive layers, films, insoles, yoga mats, floor mats, and training mats. The products are formed through injection molding, overmolding, impregnation, extrusion, rotational molding, slush molding, fiber spinning, film formation, 3D printing, or foaming. The antibacterial composition is dispersed into the polymer components of the products through melt blending with polymer materials. Preferably, the content of antibacterial powder added to the finished product is 0.32 wt%. If it is a semi-finished product, such as an antibacterial masterbatch, the antibacterial agent added is usually around 20%. The content of the antibacterial agent in the masterbatch can be increased or decreased according to application requirements.

[0044] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. All raw materials are purchased from the market. Example

[0045] Weigh 100g of zirconium oxychloride and diammonium hydrogen phosphate in a molar ratio of 2:3, add 10ppm of crystal inducing agent, and then grind them in a grinder for 30 minutes to form a uniform composite powder.

[0046] Prepare 1 L of an aqueous solution containing 0.2 mol / L sodium nitrate and 0.3 mol / L ammonium oxalate. Slowly add the uniformly ground composite powder to the aqueous solution while continuously stirring. After all the powder has been added, raise the temperature to boiling and react at boiling point for 2 hours. Then cool the solution to room temperature, add nitric acid to adjust the pH to weakly acidic, and add 5 ppm of cationic flocculant to flocculate and precipitate the suspended particles in the solution. Further dehydrate, wash, and dry the powder to obtain cubic sodium zirconium phosphate powder. Example

[0047] Weigh 10 kg of zirconium carbonate and ammonium dihydrogen phosphate in a molar ratio of 2:3, add 10 ppm of crystal inducing agent, and then grind them in a grinder for 60 min to form a uniform composite powder.

[0048] A solution of 100 L containing 0.16 mol / L of sodium nitrate and 0.2 mol / L of ammonium oxalate was prepared; the uniformly ground composite powder was slowly added to the solution, and stirring was continuously performed during the addition; after the addition was completed, the temperature was increased to boiling, and the solution was reacted for 3 hours under boiling conditions; the solution was cooled to room temperature, the pH of the solution was adjusted to weak acidity by adding nitric acid, and 15 ppm of a cationic flocculant was added to flocculate and precipitate the suspended particles in the solution; after dehydration, washing, and drying, the cubic sodium zirconium phosphate powder was obtained. Example 4

[0049] 10 g of the sodium zirconium phosphate powder prepared in Example 1 was mixed with 300 ml of deionized water, and stirring was continuously performed to form a milky white solution; silver was used as the anode and the cathode, and the areas of the cathode and the anode were the same, both being 2 cm 2 ; square wave direct current was connected, the current density was set to 0.1 A / cm 2 ; the square wave current switching frequency was 3 min / once, and the electrolysis was performed for 15 min. A silver ion loading amount of about 2 wt% of the zirconium silver phosphate antibacterial agent was prepared. Example 5

[0050] 10 g of the sodium zirconium phosphate powder prepared in Example 1 was mixed with 300 ml of deionized water, and stirring was continuously performed to form a milky white solution; zinc was used as the anode and the cathode, and the areas of the cathode and the anode were the same, both being 2 cm 2 ; square wave direct current was connected, the current density was set to 0.1 A / cm 2 ; the square wave current switching frequency was 5 min / once, and the electrolysis was performed for 30 min. A zinc ion loading amount of about 1.2 wt% of the zirconium zinc phosphate antibacterial agent was prepared. Example 6

[0051] 1 Kg of the sodium zirconium phosphate powder prepared in Example 2 was mixed with 3 L of deionized water, and stirring was continuously performed to form a milky white solution; silver and zinc were used as the two electrodes for electrolysis, and the areas of the electrodes were the same, both being 20 cm 2 ; square wave direct current was connected, the current density was set to 0.5 A / cm 2 ; the square wave current switching frequency was 5 min / once, and the electrolysis was performed for 60 min. A zinc ion loading amount of about 0.6 wt% and a silver ion loading amount of about 2 wt% of the zirconium silver zinc phosphate antibacterial agent were prepared. Example 7

[0052] 10 g of the sodium zirconium phosphate powder prepared in Example 2 was mixed with 300 ml of deionized water, and stirring was continuously performed to form a milky white solution; copper was used as the two electrodes for electrolysis, and the areas of the electrodes were the same, both being 2 cm 2 ; square wave direct current was connected, the current density was set to 0.2 A / cm 2The square wave current switching frequency is 5 min / time, and the electrolysis time is 40 min. The copper ion loading of the prepared zirconium phosphate copper antibacterial agent is about 3wt%.

[0053] It is particularly pointed out here that the loading of silver ions, zinc ions and copper ions in the zirconium phosphate sodium carrier is proportional to the electrolytic current density and the electrolysis time. Those skilled in the art can adjust the loading of silver ions, zinc ions and copper ions by adjusting the electrolytic current density and the electrolysis time according to customer requirements or product needs.

[0054] As shown in Figure 1 , 0# is a zirconium phosphate sodium powder purchased from the market, and the characteristic diffraction peak is not sharp enough, indicating that the crystal form is not complete, which is not conducive to the preparation of zirconium phosphate sodium silver antibacterial agent with high stability and not easy to discolor. Figure 1 The diffraction patterns of 1# to 4# are the samples obtained in Examples 1 to 4. As can be seen, the zirconium phosphate sodium powder prepared in Examples 1 and 2 has a sharp characteristic peak, indicating that the zirconium phosphate sodium prepared by the technical scheme of the application has a complete crystal form. Because silver ions and zinc ions replace the position of sodium ions, the loading of zinc ions and silver ions will not change the structure of zirconium phosphate sodium.

[0055] Figure 2 The micro-morphology of the zirconium phosphate sodium prepared in Example 1 is shown in the attached Figure 2 As shown in the attached

[0056] Antibacterial performance test

[0057] The antibacterial agents prepared in Examples 3 to 6 were added to polypropylene, and a double-screw granulator was used to mix the antibacterial agent with polypropylene uniformly. The addition amount was 0.5wt%, and antibacterial polypropylene was prepared. Then, according to the antibacterial plastic test standard (GB / T31402-2015), the sample was prepared, Staphylococcus aureus (ATCC25922) was selected as the test strain, and the antibacterial performance test results are shown in Table 1 and the attached Figure 3 The antibacterial agents prepared in Examples 3 to 6 have a bacteriostatic rate of >99.9%.

[0058] Table 1

[0059]

[0060] Although the present application is specifically shown and described in connection with preferred embodiments, those skilled in the art should understand that various changes in form and details can be made to the present application without departing from the spirit and scope of the present application as defined in the appended claims.

Claims

1. A method for preparing ultrafine cubic sodium zirconium phosphate, characterized in that... The preparation steps include the following: (1) Weigh out zirconium-containing compounds and phosphate-containing compounds according to the molar ratio of zirconium ions to phosphate ions of 1-2:3-4, add 10-50 ppm of crystal inducing agent, and then grind with a grinder for more than 30 minutes to form a uniformly mixed composite powder. (2) Prepare an aqueous solution containing 0.2-0.3 mol / L sodium nitrate and 0.2-0.3 mol / L ammonium oxalate; (3) Weigh the composite powder prepared in the first step according to the ratio of zirconium ions to sodium ions in the final solution of 1-1.

5. Add the composite powder slowly to the aqueous solution prepared in step (2) under continuous stirring. After all the composite powder is added, continue stirring and keep the solution boiling for 2-3 hours. (4) After the reaction is complete, cool to room temperature, adjust the pH value to weakly acidic with an acid regulator, and add 5-15 ppm of cationic organic flocculant to obtain sodium cubic zirconium phosphate precipitate; after dehydration, washing and drying, sodium cubic zirconium phosphate powder is obtained. The zirconium-containing compound refers to zirconium carbonate or zirconium oxychloride; the phosphate-containing compound is diammonium hydrogen phosphate or diammonium dihydrogen phosphate. The particle size distribution of the cubic sodium zirconium phosphate powder has a 95% region that is less than 500 nm.

2. The method for preparing ultrafine cubic sodium zirconium phosphate according to claim 1, characterized in that: The acid regulator is nitric acid.

3. The method for preparing ultrafine cubic sodium zirconium phosphate according to claim 1, characterized in that: The crystal form inducer refers to cubic sodium zirconium phosphate powder with a particle size of less than 30 nm.

4. The method for preparing ultrafine cubic sodium zirconium phosphate according to claim 1, characterized in that: In step (3), fluoride ions are added after all the composite powder has been added, and the amount of fluoride ions is 0.01-0.05 wt% of the composite powder.

5. A method for preparing an antibacterial agent using ultrafine cubic sodium zirconium phosphate as a carrier as described in claim 1, characterized in that, The preparation steps include the following: Step 1: Mix the cubic sodium zirconium phosphate powder prepared according to claim 1 with deionized water, adjust the pH of the solution to 2-3 with nitric acid, and continuously stir to form a milky white solution; the mass percentage of sodium zirconium phosphate powder in the milky white solution is 18-22 wt%. Step 2: Using silver as the anode and cathode, insert it into the milky white solution prepared in Step 1, and pass a square wave DC current to electrolyze and generate silver ions; the silver ions exchange with the sodium ions in the cubic zirconium phosphate sodium crystal to obtain the cubic zirconium phosphate silver antibacterial agent, and after dehydration, washing and drying, the ultrafine cubic zirconium phosphate silver antibacterial agent is obtained. Alternatively, zinc is used as the anode and cathode, inserted into the milky white solution prepared in step one, and a square wave DC current is passed through to electrolyze and generate zinc ions; the zinc ions exchange with the sodium ions in the cubic zirconium phosphate sodium crystals to obtain cubic zirconium phosphate zinc antibacterial agent, which is then dehydrated, washed and dried to obtain ultrafine cubic zirconium phosphate zinc antibacterial agent; Alternatively, copper is used as both the anode and cathode, and is inserted into the milky white solution prepared in step one. A square wave DC current is passed through the solution to electrolyze and generate copper ions. The copper ions exchange with the sodium ions in the sodium zirconium phosphate crystals to obtain cubic copper zirconium phosphate antibacterial agent. After filtration, washing, and drying, the ultrafine cubic copper zirconium phosphate antibacterial agent is obtained. Alternatively, silver and zinc can be used as electrodes, respectively, and inserted into the milky white solution prepared in step one. A square wave DC current is passed through to electrolyze and generate silver ions and zinc ions. The silver ions and zinc ions exchange with the sodium ions in the sodium zirconium phosphate crystals to obtain cubic zirconium phosphate silver-zinc antibacterial agent. After dehydration, washing and drying, the ultrafine cubic zirconium phosphate silver-zinc antibacterial agent is obtained. The square-wave direct current refers to a current whose direction changes periodically between the cathode and anode, i.e., the cathode becomes the anode and the anode becomes the cathode; the current direction change period of the square-wave direct current is 1-5 minutes / time; the current density is 0.05-0.5 A / cm³. 2 ; In the cubic zirconium phosphate silver antibacterial agent, cubic zirconium phosphate zinc antibacterial agent, cubic zirconium phosphate copper antibacterial agent, and cubic zirconium phosphate silver zinc antibacterial agent, silver, zinc, and copper elements exist in the form of metal ions.

6. An antibacterial product, characterized in that: The product contains 0.05-30 wt% of the antibacterial agent of claim 5, and the product is any one of antibacterial masterbatch, film, pipe, sheet, molded part, foam, fiber web, sealant, insole, and yoga mat.

7. An antibacterial product according to claim 6, characterized in that: The product also contains 0.1-1 wt% of an organic antibacterial agent.

8. An antibacterial product according to claim 7, characterized in that: The organic antibacterial agent is at least one of the following: organometallic antibacterial agents, organohalogenated antibacterial agents, alcohols, phenols, ethers, aldehydes, ketones, quinones, esters, nitriles, guanidines, organic nitro compounds, organophosphorus compounds, organic arsenic compounds, furans, pyrroles, imidazoles, benzofurans, and benzothiazoles.

Images