Sodium chlorite gel used as disinfectant and preparation process thereof
By introducing a layered bimetallic hydroxide-silicotungstic acid intercalation complex and aminophosphonic acid-modified mesoporous silica loaded with silver ions, combined with gellan gum, the preparation process of sodium chlorite gel was optimized, solving the problems of stability and antibacterial spectrum of sodium chlorite gel, and achieving efficient and stable disinfection effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANDONG GAOMI GAOYUAN CHEM IND CO LTD
- Filing Date
- 2026-03-24
- Publication Date
- 2026-04-21
AI Technical Summary
Existing sodium chlorite gel formulations have poor stability and are easily decomposed during storage. They also have a narrow antibacterial spectrum, an unstable gel network, a short shelf life, and an imperfect preservative system, resulting in poor disinfection effects.
A layered bimetallic hydroxide-silicotungstic acid intercalation complex was used as a stable carrier, and aminophosphonic acid-modified mesoporous silica was loaded with silver ions to form a synergistic antibacterial component. Combined with gellan gum as a gel matrix, the component ratio and preparation process parameters were optimized to form a stable gel network.
It significantly improves the storage stability and antibacterial effect of sodium chlorite gel, extends the shelf life, enhances the ability to kill drug-resistant bacteria and biofilms, and ensures product quality uniformity and safety.
Abstract
Description
Technical Field
[0001] This invention relates to the field of disinfectant preparation technology, specifically to sodium chlorite gel used as a disinfectant and its preparation process. Background Technology
[0002] Disinfectants have wide applications in medical and health fields, food processing, and environmental sanitation, and are important products for controlling the spread of pathogenic microorganisms and ensuring public health safety. Traditional disinfectants mainly include chlorine-containing disinfectants, peroxide disinfectants, and quaternary ammonium salt disinfectants, among which chlorine-containing disinfectants are widely used due to their low cost and broad bactericidal spectrum. However, traditional chlorine-containing disinfectants have many drawbacks, such as poor stability, easy decomposition and inactivation, strong irritating odor, corrosiveness to metals and fabrics, and potential generation of harmful byproducts. Sodium chlorite, as a novel precursor to chlorine-containing disinfectants, can slowly release chlorine dioxide gas under acidic conditions. It has advantages such as high bactericidal efficiency, long-lasting effect, and good safety, and is considered an ideal alternative to traditional chlorine-containing disinfectants. However, sodium chlorite itself has poor stability in aqueous solutions and is easily affected by factors such as light, temperature, and pH, leading to premature decomposition, loss of effective components, reduced disinfection effect, and shortened shelf life. This limits its widespread use as a gel-type disinfectant in practical applications.
[0003] Existing sodium chlorite gel formulations have significant shortcomings in their preparation processes and formulation design. On the one hand, sodium chlorite lacks an effective stable carrier in the gel system, making it prone to decomposition during storage, resulting in a short shelf life and a rapid decline in the content of active ingredients. On the other hand, sodium chlorite alone has a limited antibacterial spectrum and is ineffective against certain drug-resistant strains and biofilms, requiring synergistic effects with other antibacterial components to improve disinfection efficacy. Furthermore, existing gel matrices often use common polymer materials, resulting in an unstable gel network structure prone to problems such as layering, water separation, and viscosity changes, affecting the user experience and disinfection effectiveness. The preservative system design is also inadequate; a single preservative is difficult to maintain effectiveness over a wide pH range, easily leading to microbial contamination. More importantly, existing processes lack precise control over preparation conditions; parameters such as the order of component addition, temperature control, and stirring conditions lack systematic optimization, resulting in large batch-to-batch quality variations and difficulty in ensuring product stability.
[0004] To address the aforementioned issues, there is an urgent need to develop a novel sodium chlorite gel preparation process. This process would improve the stability of sodium chlorite by introducing functionalized carrier materials, enabling sustained and controlled release of chlorine dioxide. Furthermore, it would broaden the antibacterial spectrum through composite antibacterial components, enhancing the killing effect on drug-resistant bacteria and biofilms. Finally, it would improve product stability and uniformity by optimizing the gel matrix formulation and preparation process parameters. Layered bimetallic hydroxides, with their unique layered structure and ion exchange capacity, can serve as a stable carrier for sodium chlorite; intercalation with silicotungstic acid can further regulate the release rate. Mesoporous silica, modified with aminophosphonic acid, can effectively load silver ions, forming a stable silver complex antibacterial component that synergistically disinfects with sodium chlorite. Gellan gum, as a gel matrix, possesses advantages such as thermal reversibility, high transparency, and good stability; combined with appropriate crosslinking ions and humectants, it can form a stable gel network. By systematically optimizing process parameters such as the proportion of each component, the order of addition, temperature control, and pH adjustment, sodium chlorite gel products with good stability, strong antibacterial effect, and long shelf life can be prepared. This meets the needs of medical and health, food processing, and environmental sanitation fields for highly efficient and safe disinfectants, and has significant application value and market prospects. Summary of the Invention
[0005] The purpose of this invention is to provide sodium chlorite gel for use as a disinfectant and its preparation process, which solves the technical problems of existing sodium chlorite disinfectants such as poor stability, easy decomposition and inactivation, narrow antibacterial spectrum of single components, and poor physical stability and short shelf life of gel formulations.
[0006] The present invention achieves the above objectives through the following technical solutions: The preparation process of sodium chlorite gel used as a disinfectant includes the following steps: S1. By weight, 5.0-25.0 parts of sodium chlorite, 1.0-10.0 parts of layered bimetallic hydroxide-silicotungstic acid intercalation complex, and 0.1-3.0 parts of sodium carbonate are added to deionized water and stirred at room temperature to obtain a mixed dispersion; 0.5-8.0 parts of aminophosphonic acid modified mesoporous silica-silver complex are dispersed in deionized water and ultrasonically treated in a water bath at 25-30℃ to obtain a silver complex dispersion; 0.5-5.0 parts of gellan gum and 2.0-15.0 parts of glycerol are added to deionized water and heated and stirred in a water bath at 78-82℃ to obtain a gel matrix solution; 0.05-0.5 parts of methylparaben are dissolved in a mixed solvent of propylene glycol and deionized water to obtain a methylparaben mixed solvent solution; S2. Cool the gel matrix solution to 48-52℃, add it to the mixed dispersion under stirring, and continue stirring; cool to 34-36℃, add 0.5-5.0 parts of citric acid and sodium acetate buffer, stir, adjust the pH, and stir; add the silver complex dispersion, add the methylparaben mixed solvent solution, add 0.05-0.1 parts of potassium sorbate, add 0.05-0.1 parts of calcium chloride, and stir.
[0007] In this invention, the formation of sodium chlorite gel involves multiple mechanisms, including gel network construction, active ingredient loading, and the establishment of a stable system. Gellan gum molecules dissolve under heating conditions, allowing the polysaccharide chains to fully extend. During cooling, the molecular chains reassemble through hydrogen bonding and hydrophobic interactions, forming a three-dimensional network structure. Calcium ions act as cross-linking agents, coordinating with the carboxyl and hydroxyl groups on the gellan gum molecular chains, promoting network node formation and enhancing the gel's mechanical strength. Glycerol molecules bind to the polysaccharide chains through hydrogen bonds, filling network gaps and providing moisturizing and plasticizing effects, preventing the gel from drying and cracking. After being loaded with a layered bimetallic hydroxide intercalation complex, sodium chlorite exists in the interlayer space in an ion-exchange form. The layers shield chlorite ions, preventing direct contact with other components in the system. A buffer system adjusts the pH after gel formation, creating a weakly acidic environment. At this pH, the sodium chlorite decomposition rate is moderate, ensuring both storage stability and effective release of chlorine dioxide during use. Silver complexes are uniformly dispersed in the gel network, producing a synergistic antibacterial effect with sodium chlorite. Preservative molecules dissolve in the continuous phase, inhibiting microbial growth. The components combine through physical mixing and chemical action to form a homogeneous and stable gel system. The active ingredients remain dispersed within the gel network and are released through application, achieving a continuous disinfection effect.
[0008] According to a preferred embodiment of the present invention, in step S1, the ultrasonic treatment time in a water bath at 25-30°C is 15-20 minutes.
[0009] According to a preferred embodiment of the present invention, in step S2, the pH is adjusted to 5.5-6.5.
[0010] According to a preferred embodiment of the present invention, the preparation method of the layered bimetallic hydroxide-silicotungstic acid intercalation composite includes: A1. By weight, dissolve 35-42 parts of magnesium nitrate hexahydrate and 17-21 parts of aluminum nitrate nonahydrate in 180-220 parts of deionized water to obtain a mixed salt solution; dissolve 15-18 parts of sodium hydroxide and 9-12 parts of sodium carbonate in 180-220 parts of deionized water to obtain a mixed alkali solution; under nitrogen protection, add the mixed salt solution and mixed alkali solution dropwise to a reaction vessel containing 98-102 parts of deionized water, adjust the pH to 9.8-10.2, and after the addition is complete, crystallize in a water bath at 64-66℃ to obtain a reaction mixture; centrifuge the reaction mixture to obtain a precipitate; use... Washing with deionized water yields a magnesium aluminum carbonate LDH precursor. The magnesium aluminum carbonate LDH precursor is dispersed in 480-520 parts of a mixed solution containing sodium chloride and hydrochloric acid, the pH is adjusted to 4.0-4.5, stirred at room temperature, and centrifuged to obtain chloride LDH. 14-16 parts of silicotungstic acid are dissolved in 280-320 parts of deionized water, the pH is adjusted to 5.0-5.5, yielding a silicotungstic acid anion solution. The chloride LDH is dispersed in 180-220 parts of deionized water, and under nitrogen protection, the silicotungstic acid anion solution is added dropwise at 38-42°C, and the reaction is stirred at 50-55°C. A2. After the reaction is complete, centrifuge to obtain a precipitate; wash the precipitate with deionized water and anhydrous ethanol, vacuum dry, grind and sieve.
[0011] In this invention, the formation of a layered bimetallic hydroxide and silicotungstic acid intercalation complex is based on a dual mechanism of coprecipitation and ion exchange. First, magnesium and aluminum salts undergo a coprecipitation reaction in an alkaline aqueous solution. Metal cations combine with hydroxide ions to form a positively charged lamellar structure, with carbonate ions acting as interlayer anions to balance the charge, resulting in a magnesium-aluminum carbonate-type precursor. This precursor is then treated under acidic conditions, where carbonate ions react with hydrogen ions to generate carbon dioxide, which escapes, while chloride ions enter the interlayer and replace carbonate sites, forming a chloride-type layered bimetallic hydroxide. Subsequently, silicotungstic acid dissociates in aqueous solution to generate negatively charged polyoxometalate anions. These large anions enter the interlayer of the layered bimetallic hydroxide through ion exchange, replacing chloride ion sites. Due to the large volume and high charge density of the silicotungstic acid anions, they generate strong electrostatic interactions with the positive charges of the lamellar plates, while the interlayer hydrogen bond network further stabilizes the intercalation structure. The intercalation process is accompanied by an increase in interlayer spacing, forming a stable host-guest composite structure. In this complex, layered bimetallic hydroxide plates provide structural support as the host, while silicotungstic acid anions are embedded in the interlayer as guest atoms. Both maintain structural stability through electrostatic attraction, hydrogen bonding, and steric hindrance. This intercalation structure effectively loads chlorite ions, slowing their decomposition rate through interlayer confinement, thus achieving controlled release of the active ingredient.
[0012] According to a preferred embodiment of the present invention, in step A1, the stirring reaction at 50-55°C is carried out for 24-30 hours.
[0013] According to a preferred embodiment of the present invention, in step A2, the temperature of vacuum drying is 58-62°C.
[0014] According to a preferred embodiment of the present invention, the preparation method of the aminophosphonic acid modified mesoporous silica-silver complex includes: B1. By weight, disperse 9-11 parts of mesoporous silica in 180-220 parts of anhydrous toluene, add 14-16 parts of 3-aminopropyltriethoxysilane, and reflux at 108-112℃ under nitrogen protection. After the reaction, centrifuge to obtain a precipitate. Wash the precipitate with anhydrous toluene and anhydrous ethanol, and vacuum dry at 48-52℃ to obtain amino-modified mesoporous silica. Disperse 7-9 parts of amino-modified mesoporous silica in 140-160 parts of anhydrous ethanol, add 1.8-2.2 parts of paraformaldehyde, 11-13 parts of diethyl phosphite, and 4-6 parts of triethylamine, and stir at 58-62℃. After the reaction, centrifuge to obtain a precipitate. A precipitate was obtained; the precipitate was washed with anhydrous ethanol and dried under vacuum at 48-52℃ to obtain aminophosphonate-modified mesoporous silica; the aminophosphonate-modified mesoporous silica was dispersed in 98-102 parts of hydrochloric acid solution, stirred and dissolved at 48-52℃, and centrifuged to obtain a precipitate; the precipitate was washed with deionized water and dried under vacuum at 48-52℃ to obtain aminophosphonic acid-modified mesoporous silica; 4.5-5.5 parts of silver nitrate were dissolved in 180-220 parts of deionized water to obtain a silver nitrate solution; 5.5-6.5 parts of aminophosphonic acid-modified mesoporous silica were added to the silver nitrate solution, stirred, and the pH was adjusted to 8.0-8.5, and stirred at room temperature in the dark. B2. After the reaction is complete, centrifuge to obtain a precipitate; wash the precipitate with deionized water, dry it under vacuum at 38-42℃ in the dark, grind and sieve.
[0015] In this invention, the formation of aminophosphonic acid-modified mesoporous silica complexes with silver involves a multi-step reaction process including surface grafting, functional group transformation, and coordination bonding. The surface of mesoporous silica is rich in silanol groups, which undergo a condensation reaction with an aminosilane coupling agent under anhydrous conditions. The silanol groups dehydrate with the alkoxy groups of the silane to form siloxane bonds, and the aminopropyl group is successfully grafted onto the silica surface, yielding an amino-modified product. Subsequently, the amino group undergoes a Mannich-type reaction with paraformaldehyde and phosphite. The nitrogen atom of the amino group attacks the imine intermediate formed by formaldehyde, and the phosphorus atom of the phosphite bonds bonds with the carbon atom of the imine, forming an aminophosphonate ester structure. This ester group hydrolyzes under acidic conditions, breaking the phosphorus-oxygen-carbon bond to generate a phosphorus-oxygen-hydrogen bond, yielding free aminophosphonic acid groups. Both the nitrogen and phosphorus atoms in the aminophosphonic acid groups contain lone pairs of electrons, which can serve as coordination sites to form stable complexes with silver ions. Silver ions undergo a coordination reaction with aminophosphonic acid groups in aqueous solution. The nitrogen atom provides a lone pair of electrons to form a coordinate bond with the silver ion, while the phospho group interacts with the silver ion through the oxygen atom, resulting in a multidentate coordination structure. This multidentate coordination significantly improves the stability of silver ions, preventing their reduction or loss during storage. The high specific surface area and ordered pores of mesoporous silica provide abundant loading sites for the silver complex, and the pore confinement effect further stabilizes the state of silver ions, preventing aggregation and precipitation.
[0016] According to a preferred embodiment of the present invention, in step B1, the stirring reaction at 58-62°C is carried out for 12-14 hours.
[0017] According to a preferred embodiment of the present invention, in step B2, the time for vacuum drying at 38-42°C in the dark is 24-30 hours.
[0018] The present invention also provides a sodium chlorite gel for use as a disinfectant, prepared according to the aforementioned preparation process of sodium chlorite gel for use as a disinfectant.
[0019] The beneficial effects of this invention are as follows: The sodium chlorite gel preparation process and the resulting product provided by this invention have significant technical advantages. Firstly, by introducing a layered bimetallic hydroxide intercalated silicotungstic acid complex as a stable carrier for sodium chlorite, the technical problem of poor stability and easy decomposition of sodium chlorite in aqueous solution is effectively solved. The unique layered structure of the layered bimetallic hydroxide allows chlorite ions to be embedded between the layers, and the intercalation of silicotungstic acid further regulates the interlayer spacing and ion exchange rate, achieving controlled release of chlorine dioxide and significantly extending the effective shelf life of the product. The addition of sodium carbonate maintains the alkaline environment of the system, preventing premature decomposition of sodium chlorite during storage. The addition of a citric acid and sodium acetate buffer pair precisely adjusts the pH after gel formation, ensuring effective release during use and avoiding instability during storage. This dual stabilization mechanism significantly extends the shelf life of the product under normal temperature storage conditions, maintaining stable content of the active ingredient, and solving the problems of short shelf life and easy decomposition of traditional sodium chlorite preparations.
[0020] Secondly, this invention utilizes aminophosphonic acid-modified mesoporous silica to load silver ions, forming a stable complex that produces a synergistic antibacterial effect with sodium chlorite, significantly broadening the antibacterial spectrum and enhancing the disinfection effect. The high specific surface area and ordered pore structure of mesoporous silica provide abundant loading sites for silver ions, and the aminophosphonic acid groups form stable coordination bonds with silver ions, preventing rapid release and loss of silver ions. Silver ions and chlorine dioxide are complementary in their antibacterial mechanisms; silver ions primarily disrupt microbial cell membranes and enzyme systems, while chlorine dioxide oxidizes microbial proteins and nucleic acids. Their synergistic effect demonstrates excellent killing effects against bacteria, fungi, viruses, and biofilms, especially against drug-resistant strains. Ultrasonic dispersion ensures uniform distribution of the silver complex in the gel system, avoiding problems of excessively high or low local concentrations, and guaranteeing the uniformity and reliability of the disinfection effect.
[0021] Finally, the optimized gel matrix formulation and preparation process parameters of this invention give the product excellent physical stability and performance. Gellan gum, as the gel matrix, has advantages such as thermal reversibility, high transparency, and good mechanical strength. Glycerin acts as a humectant to prevent the gel from drying out and cracking, while calcium chloride acts as a cross-linking ion to promote gel network formation, giving the gel appropriate viscosity and adhesion, making it easy to apply and less prone to dripping. The composite preservative system of methylparaben and potassium sorbate remains effective over a wide pH range, preventing microbial contamination of the product. Precise optimization of the order of component addition and temperature control avoids the thermal decomposition of sodium chlorite and the photodecomposition of silver complexes, ensuring batch-to-batch quality stability. The resulting gel product has a uniform texture, good stability, low irritation, and high safety, making it suitable for various scenarios such as medical device surface disinfection, food processing equipment cleaning, and environmental sanitation, with broad application prospects and market value. Detailed Implementation
[0022] The following detailed embodiments are only used to further illustrate this application and should not be construed as limiting the scope of protection of this application. Those skilled in the art can make some non-essential improvements and adjustments to this application based on the above application content.
[0023] Example 1 This embodiment provides a process for preparing sodium chlorite gel for use as a disinfectant, the steps of which include: Step S1: Weigh 15g of industrial-grade sodium chlorite and add it to a 250mL beaker. Add 120g of deionized water and place the beaker on a magnetic stirrer. Stir at 300r / min for 20min at room temperature (25℃) until completely dissolved to obtain a sodium chlorite solution. Weigh 5g of layered bimetallic hydroxide-silicotungstic acid intercalation complex and add it to a 100mL beaker. Add 60g of deionized water and place the beaker on a magnetic stirrer. Stir at 500r / min for 30min at room temperature (25℃) to obtain an LDH dispersion. Weigh 1.5g of analytical-grade sodium carbonate and add it to the above sodium chlorite solution. Stir at 300r / min for 15min at room temperature (25℃). Then slowly add the LDH dispersion while stirring at 400r / min and continue stirring for 20min to obtain a mixed dispersion. Weigh 4g of amino... Phosphonic acid-modified mesoporous silica-silver complex was added to a 100mL beaker, along with 80g of deionized water. The mixture was placed in an ultrasonic cleaner at 40kHz and 200W, and ultrasonically treated in a 25℃ water bath for 15 minutes to obtain a silver complex dispersion. 2.5g of gellan gum and 8g of pharmaceutical-grade glycerin were weighed and added to a 250mL beaker, along with 150g of deionized water. The mixture was placed in a constant-temperature water bath at 80℃, and stirred at 600r / min for 40 minutes until completely dissolved to obtain a gel matrix solution. 0.2g of methylparaben was weighed and added to a 50mL beaker, along with 5g of pharmaceutical-grade propylene glycol and 15g of deionized water. The mixture was placed on a magnetic stirrer at 400r / min and stirred at room temperature (25℃) for 25 minutes until completely dissolved to obtain a methylparaben mixed solvent solution. Step S2: Remove the gel matrix solution from the 80℃ water bath and allow it to cool naturally to 50℃. Turn on the magnetic stirrer at a speed of 400 rpm. Under stirring conditions, slowly add the gel matrix solution to the mixed dispersion at a dropping rate of 5 mL / min. Continue stirring for 30 min, then allow it to cool naturally to 35℃. Weigh 1.2 g of citric acid and 0.8 g of sodium acetate and add them to a 50 mL beaker. Add 20 g of deionized water to dissolve them to obtain a buffer pair solution. Add the buffer pair solution to the above mixed solution at a dropping rate of 2 mL / min. Stir at 300 rpm for 15 min. The pH value was measured with a pH meter and adjusted to 6.0±0.1. The silver complex dispersion was added to the above mixture at a dropping rate of 3 mL / min, and the mixture was stirred at 300 r / min for 20 min. The methylparaben mixed solvent solution was added all at once, and the mixture was stirred at 300 r / min for 10 min. 0.08 g of potassium sorbate and 0.08 g of calcium chloride were weighed, dissolved in 10 g of deionized water respectively, and then added to the mixture. The mixture was stirred at 300 r / min for 30 min until the system was homogeneous, and sodium chlorite gel for use as a disinfectant was obtained. It was placed in a brown glass bottle, sealed, and stored away from light.
[0024] Preparation of layered bimetallic hydroxide-silicotungstic acid intercalation complex: Step A1: Weigh 35g of magnesium nitrate hexahydrate and 17g of aluminum nitrate nonahydrate into a 500mL beaker, add 180g of deionized water, place on a magnetic stirrer, stir at 400r / min, and stir for 30min at room temperature (25℃) until completely dissolved to obtain a mixed salt solution; weigh 15g of sodium hydroxide and 9g of sodium carbonate into a 500mL beaker, add 180g of deionized water, place on a magnetic stirrer, stir at 400r / min, and stir for 30min at room temperature (25℃) until completely dissolved to obtain a mixed alkali solution; take a 1000mL three-necked flask as the reaction vessel, add 98g of deionized water, and... A nitrogen protection device was installed, with a nitrogen flow rate of 50 mL / min. A magnetic stirrer was turned on at a stirring speed of 500 rpm. The reaction temperature was controlled at 25°C using a constant-temperature water bath. The mixed salt solution and mixed alkali solution were separately placed into two 500 mL constant-pressure dropping funnels and simultaneously added dropwise to the reaction vessel at a rate of 3 mL / min. A pH meter was used to monitor the pH in real time, and the pH of the reaction system was controlled to 10.0 ± 0.1 by adjusting the ratio of the two solutions' dropping rates. After the addition was complete, stirring continued for 30 min. Then, the reaction vessel was placed in a 64°C constant-temperature water bath with a stirring speed of 300 rpm for 4 hours to crystallize. The reaction mixture was transferred to centrifuge tubes and centrifuged at 8000 rpm for 15 min. The supernatant was discarded to obtain a precipitate. 300 g of deionized water was added to the precipitate, and the mixture was stirred at 400 rpm for 10 min. The mixture was then centrifuged again at 8000 rpm for 15 min, and this washing process was repeated three times to obtain the magnesium aluminum carbonate (MgA) LDH precursor. The MgA LDH precursor was dispersed in a 500 mL beaker, and 480 g of a mixed solution (containing 25 g sodium chloride and 5 mL of 1 mol / L hydrochloric acid) was added. The beaker was then placed on a magnetic precipitator. On a magnetic stirrer, the stirring speed was 400 r / min. The pH was adjusted to 4.2 ± 0.1 using a pH meter and stirred for 2 h at room temperature (25℃). The mixture was then centrifuged at 8000 r / min for 15 min. The supernatant was discarded, and the mixture was washed twice with 200 g of deionized water to obtain chloride ion type LDH. 14 g of silicotungstic acid was weighed and added to a 500 mL beaker. 280 g of deionized water was added, and the mixture was placed on a magnetic stirrer and stirred at 400 r / min at room temperature (25℃) for 30 min until completely dissolved. The pH was adjusted to 5.2 ± 0.1 using 0.5 mol / L sodium hydroxide solution.1. Obtain a silicotungstic acid anion solution; disperse chloride-type LDH in a 500mL three-necked flask, add 180g of deionized water, install a nitrogen protection device, nitrogen flow rate 50mL / min, turn on the magnetic stirrer, stirring speed 400r / min, and control the reaction temperature at 38℃ using a constant temperature water bath. Transfer the silicotungstic acid anion solution into a 250mL constant pressure dropping funnel and add it dropwise to the reaction vessel at a dropping rate of 2mL / min. After the addition is complete, raise the reaction temperature to 50℃, stir at 300r / min, and react for 24h. Step A2: After the reaction is complete, the reaction mixture is transferred to a centrifuge tube and centrifuged at 8000 r / min for 15 min. The supernatant is discarded to obtain the precipitate. 200 g of deionized water is added to the precipitate, and the mixture is stirred at 400 r / min for 10 min. The mixture is then centrifuged at 8000 r / min for 15 min. This washing process is repeated three times. The precipitate is then washed twice with 150 g of anhydrous ethanol. The washed precipitate is transferred to a vacuum drying oven and dried at 58 °C for 24 h under vacuum (vacuum degree ≤ -0.095 MPa). The dried product is ground in a mortar and passed through a 200-mesh sieve to obtain a layered bimetallic hydroxide-silicotungstic acid intercalated complex, which is then sealed and stored in a desiccator.
[0025] Preparation of aminophosphonic acid-modified mesoporous silica-silver complexes: Step B1: Weigh 9g of mesoporous silica (SBA-15 type, specific surface area 650m² / g, pore size 6nm) and add it to a 500mL three-necked flask. Add 180g of anhydrous toluene, turn on the magnetic stirrer, stir at 400r / min, and ultrasonically disperse for 20min to obtain a dispersion. Add 14g of 3-aminopropyltriethoxysilane (KH-550) to the dispersion, install a nitrogen protection device, nitrogen flow rate 50mL / min, install a reflux condenser, use an oil bath to control the reaction temperature at 108℃, stir at 400r / min, and reflux for 6h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The reaction mixture was then transferred to centrifuge tubes and centrifuged at 8000 rpm for 15 min. The supernatant was discarded to obtain the precipitate. 150 g of anhydrous toluene was added to the precipitate, and the mixture was stirred at 400 rpm for 10 min. The mixture was then centrifuged at 8000 rpm for 15 min, and the washing was repeated three times. The precipitate was then washed twice with 150 g of anhydrous ethanol. The washed precipitate was transferred to a vacuum drying oven and dried under vacuum at 48 °C for 18 h at a vacuum degree ≤ -0. Ammonia-modified mesoporous silica was obtained at 0.95 MPa. 7 g of amino-modified mesoporous silica was weighed and added to a 500 mL three-necked flask, along with 140 g of anhydrous ethanol. A magnetic stirrer was turned on at 400 rpm, and the mixture was ultrasonically dispersed for 15 min. 1.8 g of paraformaldehyde, 11 g of diethyl phosphite, and 4 g of triethylamine were added to the dispersion. The reaction was carried out at a constant temperature of 58 °C using a water bath, with a stirring speed of 400 rpm, for 12 h. After the reaction was complete, the reaction mixture was transferred to centrifuge tubes and centrifuged at 800 rpm. Centrifuge at 0 r / min for 15 min, discard the supernatant to obtain a precipitate; add 100 g of anhydrous ethanol to the precipitate, stir at 400 r / min, wash for 10 min, centrifuge at 8000 r / min for 15 min, repeat washing 3 times; transfer the washed precipitate to a vacuum drying oven and vacuum dry at 48℃ for 18 h, vacuum degree ≤ -0.095 MPa, to obtain aminophosphonate-modified mesoporous silica; disperse the aminophosphonate-modified mesoporous silica in a 500 mL beaker, add 98 g of hydrochloric acid solution (concentration 0.5 mol / L of the solution was placed on a magnetic stirrer at 400 rpm and the reaction temperature was controlled at 48°C using a constant temperature water bath for 2 hours of hydrolysis. After hydrolysis, the reaction mixture was transferred to centrifuge tubes and centrifuged at 8000 rpm for 15 minutes. The supernatant was discarded to obtain the precipitate. 200 g of deionized water was added to the precipitate, and the mixture was washed at 400 rpm for 10 minutes. The mixture was then centrifuged at 8000 rpm for 15 minutes, and the washing was repeated until the pH of the filtrate was neutral. The washed precipitate was transferred to a vacuum drying oven and dried under vacuum at 48°C for 24 hours at a vacuum degree ≤ -0.095 MPa. a) Obtain aminophosphonic acid-modified mesoporous silica; weigh 4.5g of silver nitrate and add it to a 500mL beaker, add 180g of deionized water, place it on a magnetic stirrer, stir at 300r / min, and stir at room temperature (25℃) for 20min until completely dissolved to obtain a silver nitrate solution; weigh 5.5g of aminophosphonic acid-modified mesoporous silica and add it to a 500mL beaker, add the above silver nitrate solution, turn on the magnetic stirrer, stir at 400r / min, and stir at room temperature (25℃) for 30min, adjust the pH to 8.0±0.1 with 0.1mol / L sodium hydroxide solution, wrap the flask with aluminum foil to protect it from light, stir at 300r / min, and stir at room temperature (25℃) in the dark for 12h. Step B2: After the reaction is complete, transfer the reaction mixture to a centrifuge tube and centrifuge at 8000 r / min for 15 min. Discard the supernatant to obtain the precipitate. Add 200 g of deionized water to the precipitate, stir at 400 r / min, wash for 10 min, centrifuge at 8000 r / min for 15 min, and repeat the washing process three times until no silver ions are detected in the filtrate (using sodium chloride solution for detection). Transfer the washed precipitate to a vacuum drying oven and dry it at 38℃ in the dark for 24 h, with a vacuum degree ≤ -0.095 MPa. Grind the dried product in a mortar and pass it through a 200-mesh sieve to obtain the aminophosphonic acid modified mesoporous silica-silver complex. Store it in a brown glass bottle, seal it, and protect it from light in a desiccator.
[0026] Example 2 The specific implementation method is the same as in Example 1, except for the preparation of the layered bimetallic hydroxide-silicotungstic acid intercalation complex: Step A1: Dissolve 42g of magnesium nitrate hexahydrate and 21g of aluminum nitrate nonahydrate in 220g of deionized water to obtain a mixed salt solution. Dissolve 18g of sodium hydroxide and 12g of sodium carbonate in 220g of deionized water to obtain a mixed alkali solution. Under nitrogen protection, add the mixed salt solution and mixed alkali solution dropwise to a reaction vessel containing 102g of deionized water. Adjust the pH to 10.2. After the addition is complete, crystallize in a 66℃ water bath for 5 hours to obtain a reaction mixture. Centrifuge the reaction mixture to obtain a precipitate, and wash the precipitate with deionized water. Magnesium aluminum carbonate type LDH precursor was obtained by dispersing the magnesium aluminum carbonate type LDH precursor in 520g of a mixed solution containing sodium chloride and hydrochloric acid, adjusting the pH to 4.5, stirring at room temperature for 3h, and centrifuging to obtain chloride ion type LDH. 16g of silicotungstic acid was dissolved in 320g of deionized water, and the pH was adjusted to 5.5 to obtain silicotungstic acid anion solution. Chloride ion type LDH was dispersed in 220g of deionized water, and the silicotungstic acid anion solution was added dropwise at 42℃ under nitrogen protection, and the reaction was stirred at 55℃ for 30h. Step A2: After the reaction is complete, centrifuge to obtain the precipitate, wash the precipitate with deionized water and anhydrous ethanol, dry it under vacuum at 62°C, grind and sieve to obtain the layered bimetallic hydroxide-silicotungstic acid intercalation complex.
[0027] Preparation of aminophosphonic acid-modified mesoporous silica-silver complexes: Step B1: 11g of mesoporous silica was dispersed in 220g of anhydrous toluene, and 16g of 3-aminopropyltriethoxysilane was added. The mixture was refluxed at 112℃ under nitrogen protection for 8 hours. After the reaction, the precipitate was obtained by centrifugation. The precipitate was washed with anhydrous toluene and anhydrous ethanol, and dried under vacuum at 52℃ to obtain amino-modified mesoporous silica. 9g of amino-modified mesoporous silica was dispersed in 160g of anhydrous ethanol, and 2.2g of paraformaldehyde, 13g of diethyl phosphite, and 6g of triethylamine were added. The mixture was stirred at 62℃ for 14 hours. After the reaction, the precipitate was obtained by centrifugation. The precipitate was washed with anhydrous ethanol and dried under vacuum at 52°C to obtain aminophosphonate-modified mesoporous silica. The aminophosphonate-modified mesoporous silica was dispersed in 102g hydrochloric acid solution and hydrolyzed by stirring at 52°C for 3h. The precipitate was separated by centrifugation and washed with deionized water. The precipitate was dried under vacuum at 52°C to obtain aminophosphonate-modified mesoporous silica. 5.5g silver nitrate was dissolved in 220g deionized water to obtain silver nitrate solution. 6.5g aminophosphonate-modified mesoporous silica was added to the silver nitrate solution, stirred, and the pH was adjusted to 8.5. The solution was stirred at room temperature in the dark for 14h.
[0028] Step B2: Preparation of aminophosphonic acid modified mesoporous silica-silver complex: After the reaction, the precipitate was obtained by centrifugation. The precipitate was washed with deionized water, dried in vacuum at 42℃ for 30 h in the dark, and then ground and sieved to obtain aminophosphonic acid modified mesoporous silica-silver complex.
[0029] Preparation process of sodium chlorite gel used as a disinfectant: Step S1: Add 25g sodium chlorite, 10g layered bimetallic hydroxide-silicotungstic acid intercalation complex, and 3g sodium carbonate to deionized water and stir at room temperature to obtain a mixed dispersion. Disperse 8g aminophosphonic acid modified mesoporous silica-silver complex in deionized water and sonicate in a 30℃ water bath for 20min to obtain a silver complex dispersion. Add 5g gellan gum and 15g glycerol to deionized water and heat and stir in a 82℃ water bath to obtain a gel matrix solution. Dissolve 0.5g methylparaben in a mixed solvent of propylene glycol and deionized water to obtain a methylparaben mixed solvent solution. Step S2: Cool the gel matrix solution to 52°C, add it to the mixed dispersion under stirring, continue stirring, cool to 36°C, add 5g of citric acid and sodium acetate buffer, stir, adjust the pH to 6.5, stir, add silver complex dispersion, add methylparaben mixed solvent solution, add 0.1g of potassium sorbate, add 0.1g of calcium chloride, and stir to obtain sodium chlorite gel for use as a disinfectant.
[0030] Example 3 The specific implementation method is the same as in Example 1, except for the preparation of the layered bimetallic hydroxide-silicotungstic acid intercalation complex: Step A1: Dissolve 38g of magnesium nitrate hexahydrate and 19g of aluminum nitrate nonahydrate in 200g of deionized water to obtain a mixed salt solution. Dissolve 16g of sodium hydroxide and 10g of sodium carbonate in 200g of deionized water to obtain a mixed alkali solution. Under nitrogen protection, add the mixed salt solution and mixed alkali solution dropwise to a reaction vessel containing 100g of deionized water. Adjust the pH to 10.0. After the addition is complete, crystallize in a 65℃ water bath for 4.5h to obtain a reaction mixture. Centrifuge the reaction mixture to obtain a precipitate, and wash the precipitate with deionized water. Magnesium aluminum carbonate LDH precursor was obtained by dispersing it in 500g of a mixed solution containing sodium chloride and hydrochloric acid, adjusting the pH to 4.3, stirring at room temperature for 2.5h, and centrifuging to obtain chloride ion LDH. 15g of silicotungstic acid was dissolved in 300g of deionized water, and the pH was adjusted to 5.3 to obtain a silicotungstic acid anion solution. The chloride ion LDH was dispersed in 200g of deionized water, and the silicotungstic acid anion solution was added dropwise at 40℃ under nitrogen protection, and the reaction was stirred at 52℃ for 27h. Step A2: After the reaction is complete, centrifuge to obtain the precipitate, wash the precipitate with deionized water and anhydrous ethanol, dry it under vacuum at 60°C, grind and sieve to obtain the layered bimetallic hydroxide-silicotungstic acid intercalation complex.
[0031] Preparation of aminophosphonic acid-modified mesoporous silica-silver complexes: Step B1: Disperse 10g of mesoporous silica in 200g of anhydrous toluene, add 15g of 3-aminopropyltriethoxysilane, and reflux at 110℃ under nitrogen protection for 7h. After the reaction, centrifuge to obtain the precipitate, wash the precipitate with anhydrous toluene and anhydrous ethanol, and dry it under vacuum at 50℃ to obtain amino-modified mesoporous silica. Disperse 8g of amino-modified mesoporous silica in 150g of anhydrous ethanol, add 2g of paraformaldehyde, 12g of diethyl phosphite and 5g of triethylamine, and stir at 60℃ for 13h. After the reaction, centrifuge to obtain the precipitate. The precipitate was washed with anhydrous ethanol and dried under vacuum at 50°C to obtain aminophosphonate-modified mesoporous silica. The aminophosphonate-modified mesoporous silica was dispersed in 100g hydrochloric acid solution and hydrolyzed by stirring at 50°C for 2.5h. The precipitate was separated by centrifugation and washed with deionized water. The precipitate was dried under vacuum at 50°C to obtain aminophosphonate-modified mesoporous silica. 5g silver nitrate was dissolved in 200g deionized water to obtain silver nitrate solution. 6g aminophosphonate-modified mesoporous silica was added to the silver nitrate solution, stirred, and the pH was adjusted to 8.2. The solution was stirred at room temperature in the dark for 13h. Step B2: After the reaction is complete, centrifuge to obtain the precipitate, wash the precipitate with deionized water, dry it under vacuum at 40°C for 27 hours in the dark, grind and sieve to obtain aminophosphonic acid modified mesoporous silica-silver complex.
[0032] Preparation process of sodium chlorite gel used as a disinfectant: Step S1: Add 20g sodium chlorite, 7g layered bimetallic hydroxide-silicotungstic acid intercalation complex, and 2g sodium carbonate to deionized water and stir at room temperature to obtain a mixed dispersion. Disperse 6g aminophosphonic acid modified mesoporous silica-silver complex in deionized water and sonicate in a 28℃ water bath for 18min to obtain a silver complex dispersion. Add 4g gellan gum and 12g glycerol to deionized water and heat and stir in a 81℃ water bath to obtain a gel matrix solution. Dissolve 0.4g methylparaben in a mixed solvent of propylene glycol and deionized water to obtain a methylparaben mixed solvent solution. Step S2: Cool the gel matrix solution to 51°C, add it to the mixed dispersion under stirring, continue stirring, cool to 35°C, add 3g of citric acid and sodium acetate buffer, stir, adjust the pH to 6.2, stir, add silver complex dispersion, add methylparaben mixed solvent solution, add 0.09g of potassium sorbate, add 0.09g of calcium chloride, and stir to obtain sodium chlorite gel for use as a disinfectant.
[0033] Comparative Example 1 The specific implementation method is the same as in Example 1, except that no layered bimetallic hydroxide-silicotungstic acid intercalation complex is added, while the remaining steps and parameters are consistent with those in Example 1.
[0034] Comparative Example 2 The specific implementation method is the same as in Example 1, except that aminophosphonic acid-modified mesoporous silica-silver complex is not added, while the remaining steps and parameters are consistent with those in Example 1.
[0035] Comparative Example 3 The specific implementation method is the same as in Example 1, except that the layered bimetallic hydroxide-silicotungstic acid intercalation complex and aminophosphonic acid modified mesoporous silica-silver complex are not added, while the remaining steps and parameters are consistent with those in Example 1.
[0036] Performance testing The sodium chlorite gels prepared in Examples 1-3 and Comparative Examples 1-3 as disinfectants were subjected to performance testing according to the following method, which included the following steps: Test method for Staphylococcus aureus kill rate: Prepare a Staphylococcus aureus ATCC6538 bacterial suspension and adjust the bacterial concentration to 1×10⁻⁶. 8 CFU / mL, take 0.1 mL of bacterial suspension and add it to 0.9 mL of sodium chlorite gel sample, mix thoroughly, and after 5 min, immediately add 5 mL of neutralizing agent to terminate the reaction. The neutralizing agent is phosphate buffer containing 0.5% sodium thiosulfate, pH 7.2. Take 1 mL of the neutralized solution for serial dilution, select an appropriate dilution and spread it on nutrient agar plates. After incubation at 37℃ for 48 h, count the number of colonies. At the same time, a control group is set up. The control group uses sterile deionized water instead of gel sample. Calculate the kill rate according to the formula. The kill rate is equal to the number of viable bacteria in the control group minus the number of viable bacteria in the experimental group, divided by the number of viable bacteria in the control group, and then multiplied by 100%. Each group of experiments is repeated 3 times and the average value is taken.
[0037] Method for testing the kill rate of Escherichia coli: Prepare an Escherichia coli 8099 bacterial suspension and adjust the bacterial concentration to 1×10⁻⁶. 8 CFU / mL, take 0.1 mL of bacterial suspension and add it to 0.9 mL of sodium chlorite gel sample, mix thoroughly, and after 5 min, immediately add 5 mL of neutralizing agent to terminate the reaction. The neutralizing agent is phosphate buffer containing 0.5% sodium thiosulfate, pH 7.2. Take 1 mL of the neutralized solution for serial dilution, select an appropriate dilution and spread it on nutrient agar plates. After incubation at 37℃ for 48 h, count the number of colonies. At the same time, a control group is set up. The control group uses sterile deionized water instead of gel sample. Calculate the kill rate according to the formula. The kill rate is equal to the number of viable bacteria in the control group minus the number of viable bacteria in the experimental group, divided by the number of viable bacteria in the control group, and then multiplied by 100%. Each group of experiments is repeated 3 times and the average value is taken.
[0038] Test method for Candida albicans kill rate: Prepare a Candida albicans ATCC10231 bacterial suspension, and adjust the bacterial concentration to 1×10⁻⁶. 7CFU / mL, take 0.1 mL of bacterial suspension and add it to 0.9 mL of sodium chlorite gel sample, mix thoroughly, and after 5 min, immediately add 5 mL of neutralizing agent to terminate the reaction. The neutralizing agent is phosphate buffer containing 0.5% sodium thiosulfate, pH 7.2. Take 1 mL of the neutralized solution and perform serial dilutions. Select an appropriate dilution and spread it on Sabouraud agar plates. After incubation at 28℃ for 72 h, count the number of colonies. At the same time, a control group is set up. The control group uses sterile deionized water instead of gel sample. Calculate the kill rate according to the formula. The kill rate is equal to the number of viable bacteria in the control group minus the number of viable bacteria in the experimental group, divided by the number of viable bacteria in the control group, and then multiplied by 100%. Each group of experiments is repeated 3 times and the average value is taken.
[0039] Sodium chlorite content retention rate test method: Each sodium chlorite gel sample was placed in a 54℃ constant temperature oven for accelerated aging test. Samples were taken at 0d and 14d respectively. The effective content of sodium chlorite was determined by iodometric titration. 5g of sample was accurately weighed into an iodine flask, dissolved in 50mL of deionized water, 10mL of 10% potassium iodide solution was added, and 10mL of 2mol / L sulfuric acid solution was added. The sample was placed in the dark for 10min, titrated with 0.1mol / L sodium thiosulfate standard solution until pale yellow, 1mL of starch indicator was added, and titration continued until the blue color disappeared. The volume of sodium thiosulfate consumed was recorded, and the sodium chlorite content was calculated. The content retention rate was equal to the content at 14d divided by the content at 0d and then multiplied by 100%. Each test was repeated 3 times and the average value was taken.
[0040] Test method for chlorine dioxide cumulative release over 24 hours: Weigh 10g of sodium chlorite gel sample and place it in a 100mL sealed container. Leave space at the top of the container for gas collection. Use a chlorine dioxide detector to measure the concentration of chlorine dioxide released at different time points. Record the concentration values at 0h, 1h, 2h, 4h, 8h, 12h, and 24h. The test temperature is 25℃ and the relative humidity is 50%. Calculate the chlorine dioxide release based on the container volume and concentration value. The cumulative release over 24 hours is equal to the total release over 24 hours divided by the theoretical maximum release and then multiplied by 100%. Each test is repeated 3 times and the average value is taken.
[0041] Storage stability test method for sodium chlorite retention rate: Each sodium chlorite gel sample was sealed and stored in a constant temperature and humidity chamber at 25℃. Samples were taken at 0d and 90d. The effective content of sodium chlorite was determined by iodometric titration. 5g of sample was accurately weighed into an iodine flask, dissolved in 50mL of deionized water, 10mL of 10% potassium iodide solution was added, and 10mL of 2mol / L sulfuric acid solution was added. The sample was placed in the dark for 10min, titrated with 0.1mol / L sodium thiosulfate standard solution until pale yellow, 1mL of starch indicator was added, and titration continued until the blue color disappeared. The volume of sodium thiosulfate consumed was recorded, and the sodium chlorite content was calculated. The storage stability retention rate was equal to the 90d content divided by the 0d content and then multiplied by 100%. Each test was repeated 3 times and the average value was taken.
[0042] Test results: Table 1: Test results of each embodiment and comparative example ; As can be seen from Table 1, the sodium chlorite gels prepared in Examples 1-3 are significantly better than those in Comparative Examples 1-3 in all performance indicators, effectively solving the technical problems of poor stability, short-lasting antibacterial effect, and easy decomposition of active ingredients in existing sodium chlorite disinfectants.
[0043] In terms of antibacterial performance, Examples 1-3 all achieved a kill rate of over 99.95% against Staphylococcus aureus, Escherichia coli, and Candida albicans within 5 minutes, while Comparative Example 1 showed 99.5%, 99.3%, and 98.8%, respectively; Comparative Example 2 showed 99.2%, 99.0%, and 98.5%, respectively; and Comparative Example 3 showed only 95.3%, 94.8%, and 93.2%, respectively. This indicates that the coexistence of the layered bimetallic hydroxide-silicotungstic acid intercalated complex and the aminophosphonic acid modified mesoporous silica-silver complex produced a significant synergistic antibacterial effect. The slow release of silver ions and the release of chlorine dioxide from sodium chlorite form a dual antibacterial mechanism, which greatly enhances the rapid killing ability.
[0044] In terms of stability, after accelerated aging at 54°C for 14 days, the sodium chlorite content retention rate of Examples 1-3 reached 93.8-94.5%, while that of Comparative Example 1 was only 68.5% and that of Comparative Example 3 was only 62.3%. This indicates that the layered bimetallic hydroxide-silicotungstic acid intercalation complex effectively protects sodium chlorite from thermal decomposition through the interlayer confinement effect. The intercalation structure of silicotungstic acid anions forms a physical barrier to delay the degradation of the active ingredient. The lack of this component in Comparative Example 1 led to a sharp decrease in stability.
[0045] In terms of sustained-release performance, the cumulative release of chlorine dioxide in Examples 1-3 over 24 hours was 85.3-87.5%, while that in Comparative Example 3 was as high as 95.2%. This indicates that the presence of the two functional components effectively controlled the release rate of chlorine dioxide, preventing the active ingredient from being released too quickly and thus shortening the disinfection time. The release amounts of Comparative Examples 1 and 2 were 92.8% and 86.5%, respectively, further demonstrating that the layered bimetallic hydroxide intercalation complex made a more significant contribution to the sustained-release performance.
[0046] In terms of long-term storage stability, after 90 days of storage at 25°C, the sodium chlorite retention rate of Examples 1-3 reached 91.5-92.8%, while that of Comparative Examples 1, 2, and 3 was 75.3%, 89.5%, and 70.2%, respectively. This indicates that the synergistic effect of the two functional components enables the product to maintain a stable effective content during long-term storage, ensuring the durability of the disinfection effect.
[0047] Based on the above data, Examples 1-3 provide stability protection and sustained-release control through layered bimetallic hydroxide-silicotungstic acid intercalation complex, and provide synergistic antibacterial and auxiliary sustained-release functions through aminophosphonic acid modified mesoporous silica-silver complex. The synergistic effect of these three components solves the technical problems of easy decomposition of active ingredients, short-lasting antibacterial effect and poor storage stability of existing sodium chlorite disinfectants, and achieves efficient, stable and long-lasting disinfection effect.
[0048] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.
Claims
1. A process for preparing sodium chlorite gel for use as a disinfectant, characterized in that the steps include... include: S1. By weight, 5.0-25.0 parts of sodium chlorite, 1.0-10.0 parts of layered bimetallic hydroxide-silicotungstic acid intercalation complex, and 0.1-3.0 parts of sodium carbonate are added to deionized water and stirred at room temperature to obtain a mixed dispersion; 0.5-8.0 parts of aminophosphonic acid modified mesoporous silica-silver complex are dispersed in deionized water and ultrasonically treated in a water bath at 25-30℃ to obtain a silver complex dispersion; 0.5-5.0 parts of gellan gum and 2.0-15.0 parts of glycerol are added to deionized water and heated and stirred in a water bath at 78-82℃ to obtain a gel matrix solution; 0.05-0.5 parts of methylparaben are dissolved in a mixed solvent of propylene glycol and deionized water to obtain a methylparaben mixed solvent solution; S2. Cool the gel matrix solution to 48-52℃, add it to the mixed dispersion under stirring, and continue stirring; cool to 34-36℃, add 0.5-5.0 parts of citric acid and sodium acetate buffer, stir, adjust the pH, and stir again; Add the silver complex dispersion, methylparaben mixed solvent solution, 0.05-0.1 parts potassium sorbate, and 0.05-0.1 parts calcium chloride, and stir. The preparation method of the layered bimetallic hydroxide-silicotungstic acid intercalation complex includes: A1. By weight, dissolve 35-42 parts of magnesium nitrate hexahydrate and 17-21 parts of aluminum nitrate nonahydrate in 180-220 parts of deionized water to obtain a mixed salt solution; dissolve 15-18 parts of sodium hydroxide and 9-12 parts of sodium carbonate in 180-220 parts of deionized water to obtain a mixed alkali solution; under nitrogen protection, add the mixed salt solution and mixed alkali solution dropwise to a reaction vessel containing 98-102 parts of deionized water, adjust the pH to 9.8-10.2, and after the addition is complete, crystallize in a water bath at 64-66℃ to obtain a reaction mixture; centrifuge the reaction mixture to obtain a precipitate; use... Washing with deionized water yields a magnesium aluminum carbonate LDH precursor. The magnesium aluminum carbonate LDH precursor is dispersed in 480-520 parts of a mixed solution containing sodium chloride and hydrochloric acid, the pH is adjusted to 4.0-4.5, stirred at room temperature, and centrifuged to obtain chloride LDH. 14-16 parts of silicotungstic acid are dissolved in 280-320 parts of deionized water, the pH is adjusted to 5.0-5.5, yielding a silicotungstic acid anion solution. The chloride LDH is dispersed in 180-220 parts of deionized water, and under nitrogen protection, the silicotungstic acid anion solution is added dropwise at 38-42°C, and the reaction is stirred at 50-55°C. A2. After the reaction is complete, centrifuge to obtain a precipitate; wash the precipitate with deionized water and anhydrous ethanol, vacuum dry, grind and sieve.
2. The preparation process of sodium chlorite gel as a disinfectant according to claim 1, characterized in that, In step S1, the ultrasonic treatment in a water bath at 25-30℃ takes 15-20 minutes.
3. The preparation process of sodium chlorite gel as a disinfectant according to claim 1, characterized in that, In step S2, adjust the pH to 5.5-6.
5.
4. The preparation process of sodium chlorite gel as a disinfectant according to claim 1, characterized in that, In step A1, the reaction is stirred at 50-55℃ for 24-30 hours.
5. The preparation process of sodium chlorite gel as a disinfectant according to claim 1, characterized in that, In step A2, the vacuum drying temperature is 58-62℃.
6. The preparation process of sodium chlorite gel as a disinfectant according to claim 1, characterized in that, The preparation method of the aminophosphonic acid modified mesoporous silica-silver complex includes: B1. By weight, disperse 9-11 parts of mesoporous silica in 180-220 parts of anhydrous toluene, add 14-16 parts of 3-aminopropyltriethoxysilane, and reflux at 108-112℃ under nitrogen protection. After the reaction, centrifuge to obtain a precipitate. Wash the precipitate with anhydrous toluene and anhydrous ethanol, and vacuum dry at 48-52℃ to obtain amino-modified mesoporous silica. Disperse 7-9 parts of amino-modified mesoporous silica in 140-160 parts of anhydrous ethanol, add 1.8-2.2 parts of paraformaldehyde, 11-13 parts of diethyl phosphite, and 4-6 parts of triethylamine, and stir at 58-62℃. After the reaction, centrifuge to obtain a precipitate. A precipitate was obtained; the precipitate was washed with anhydrous ethanol and dried under vacuum at 48-52℃ to obtain aminophosphonate-modified mesoporous silica; the aminophosphonate-modified mesoporous silica was dispersed in 98-102 parts of hydrochloric acid solution, stirred and dissolved at 48-52℃, and centrifuged to obtain a precipitate; the precipitate was washed with deionized water and dried under vacuum at 48-52℃ to obtain aminophosphonic acid-modified mesoporous silica; 4.5-5.5 parts of silver nitrate were dissolved in 180-220 parts of deionized water to obtain a silver nitrate solution; 5.5-6.5 parts of aminophosphonic acid-modified mesoporous silica were added to the silver nitrate solution, stirred, and the pH was adjusted to 8.0-8.5, and stirred at room temperature in the dark. B2. After the reaction is complete, centrifuge to obtain a precipitate; wash the precipitate with deionized water, dry it under vacuum at 38-42℃ in the dark, grind and sieve.
7. The preparation process of sodium chlorite gel as a disinfectant according to claim 6, characterized in that, In step B1, the reaction is stirred at 58-62℃ for 12-14 hours.
8. The preparation process of sodium chlorite gel as a disinfectant according to claim 6, characterized in that, In step B2, the vacuum drying time at 38-42℃ in the dark is 24-30 hours.
9. A sodium chlorite gel for use as a disinfectant, characterized in that, The sodium chlorite gel used as a disinfectant is prepared according to the preparation process of sodium chlorite gel used as a disinfectant according to any one of claims 1-8.
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