CN115073958B - Paint additive with antibacterial and antiviral functions and preparation method and application thereof - Google Patents

Abstract

The invention discloses a preparation method of a coating additive with antibacterial and antiviral functions, which comprises the following steps: adding a silver nitrate solution into a nonylphenol polyoxyethylene ether solution, and simultaneously adding a coordination agent to construct a water phase; adding the nonylphenol polyoxyethylene ether solution into the cyclohexane solution, and uniformly mixing to construct an oil phase; mixing the water phase and the oil phase, and adding ammonia water and deionized water to prepare a W/O reverse microemulsion system; mixing tetraethyl silicate solution and N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixed solution into a W/O reverse microemulsion system, adding the N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, and uniformly stirring to obtain an intermediate product; and heating and stirring the intermediate product in the nitrogen atmosphere to obtain a solid, and carrying out post-treatment on the solid to obtain the coating additive. The preparation method can improve the content of silver ions in the paint additive, thereby improving the antibacterial and antiviral effects of the paint additive.

Description

Paint additive with antibacterial and antiviral functions and preparation method and application thereof

Technical Field

The invention relates to the technical field of antibacterial and antiviral of coatings, in particular to a preparation method of a coating additive with antibacterial and antiviral functions, the coating additive prepared by the preparation method and application of the coating additive in coatings.

Background

The paint is a common surface decoration material and has wide application in the fields of vehicles, decoration, military, traffic, buildings and the like. The building coating is one of four major products for the key development of chemical building materials, and the research and development of high-performance antibacterial coatings are widely regarded by various countries. Architectural coatings, the most commonly used building materials, account for a large share of the coating market. Driven by the modern health consumption concept, along with the improvement of living standard and weight, people gradually know the true meaning and application of the antibacterial coating, and the consumer market in China presents the situation of more and more vigorous demand of the antibacterial coating.

China scientists have tracked the research and application of international antibacterial coatings more than ten years ago, but the research on the antiviral coatings is very little, and particularly in China, the research on the antibacterial and antiviral coatings and the production technology are still basically at the level of the early stage of the development of architectural coatings. For example, CN 102499255A discloses a method for preparing a novel silver ion molecular sieve antibacterial agent, which comprises the steps of firstly preparing a molecular sieve from raw materials such as a silicon source, an aluminum source, a template agent and alkali, and then loading silver ions onto the molecular sieve through ion exchange. However, the content of silver ions in the silver-loaded molecular sieve prepared by the method is not very high, and the using amount of the silver-loaded molecular sieve needs to be increased if the effective antibacterial and antiviral efficiency of the coating meets the national standard in the actual use process. In addition, the stability of the carried silver ions is not enough, and the silver ions are easy to be oxidized and separated out in certain coatings, so that the use cost and the risk of unqualified effective rate of antibacterial and antiviral properties are greatly increased.

Disclosure of Invention

One of the purposes of the invention is to provide a preparation method of a paint additive with antibacterial and antiviral functions and the paint additive prepared by the preparation method, and the preparation method can improve the content of silver ions in the paint additive, thereby improving the antibacterial and antiviral effects of the paint additive.

In order to achieve the purpose, the invention adopts the following technical scheme:

the preparation method of the paint additive with antibacterial and antiviral functions comprises the following steps:

s10, adding a silver nitrate solution into a nonylphenol polyoxyethylene ether solution, adding a coordination agent, and uniformly mixing to construct a water phase of the reverse microemulsion; the silver ions can be prevented from precipitating through the coordination of serinol and tromethamine to the silver ions, and the step can simultaneously construct the water phase of the reverse microemulsion;

s20, adding the nonylphenol polyoxyethylene ether solution into the cyclohexane solution, and uniformly mixing to construct an oil phase of the reverse microemulsion;

s30, mixing the water phase and the oil phase, and adding ammonia water and deionized water to prepare a W/O reverse microemulsion system, namely a water-in-oil micelle can be formed in the mixed solution; adding ammonia water and deionized water to ensure that the pH value of the solution is alkaline and prepare for the next hydrolysis of tetraethyl silicate;

s40, mixing a tetraethyl silicate solution with a part of N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixed solution into a W/O reverse microemulsion system, adding the other part of N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, and uniformly stirring to obtain an intermediate product;

tetraethyl silicate is silicon source, N- [3- (trimethoxysilyl) propyl group is added]Ethylene diamine, which modifies the tetraethyl silicate groups, promotes hydrolysis and silica globule formation. Adding tetraethyl silicate and N- [3- (trimethoxysilyl) propyl]The ethylene diamine is used for introducing a silicon source, mesoporous silicon dioxide is generated under an alkaline condition, tetraethyl silicate is added after full stirring, the hydrolysis at the initial stage is mainly concentrated on an oil-water phase interface of reverse microemulsion due to lipophilicity, the ethoxy group of the tetraethyl silicate is hydrolyzed into hydroxyl group along with the progress of the hydrolysis reaction, so that the hydrophilicity of the tetraethyl silicate is gradually enhanced, the tetraethyl silicate gradually enters a water phase to be continuously hydrolyzed, and finally the tetraethyl silicate is crosslinked with each other to form SiO of reticular gel ₂ Its H dimensional space structure is Ag ^＋ The complex is coated in the pore canal, N- [3- (trimethoxysilyl) propyl]The ethylenediamine can be used as an auxiliary silicon source, and silane (tetraethyl silicate) can be used for preparing aminosilane (N- [3- (trimethoxysilyl) propyl)]Ethylenediamine) modified surface to further hydrolyze and condense Ag ^＋ The complex compound is coated in the pore canal; the invention relates to a method for preparing N- [3- (trimethoxysilyl) propyl group]The ethylenediamine solution is added in two steps to ensure that there is sufficient silicon source to hydrolyze to produce mesoporous silica.

S50, heating and stirring the intermediate product in the nitrogen atmosphere to obtain a solid, and washing and drying the solid to obtain the coating additive; specifically, heating and stirring the intermediate product at 90 to 180 ℃ for 2 to 12 hours in a nitrogen atmosphere, taking out the solid, centrifugally washing the solid with ethanol and acetone for 3~5 times, removing residual organic matters, centrifugally washing the solid with deionized water, and drying to obtain the coating additive.

The invention utilizes a method of reverse microemulsion to synthesize a mesoporous silica molecular sieve capable of coating silver ions by rapid hydrolysis and condensation of silane on the modified surface of aminosilane, the silver ions are introduced into a pore channel structure of the molecular sieve while the mesoporous silica molecular sieve is synthesized, and the coordination of a coordination agent to the silver ions is utilized, so that the precipitation of the silver ions can be prevented, the slow release of the silver ions is realized, the antibacterial and antiviral durability is improved, the silver-loaded molecular sieve has better antibacterial and antiviral performance, is not easy to generate drug resistance, has good compatibility and stability with coating, and can be used for preparing antibacterial and antiviral coating.

In step S10, the molar concentration of the silver nitrate solution is 10 to 100mmol/L, and the specific addition amount is 5 to 500 mL.

Further, the polyoxyethylene nonylphenol ether is selected from any one of polyoxyethylene nonylphenol ether (Type NP-7), polyoxyethylene nonylphenol ether (Type NP-9), and polyoxyethylene nonylphenol ether (Type NP-10).

In step S10, the nonylphenol polyoxyethylene ether solution is added in an amount of 2 to 10mL, and the concentration is 10 to 100 mmol/L.

Further, the complexing agent consists of serinol and tromethamine, and the molar ratio of the serinol to the tromethamine to the nonylphenol polyoxyethylene ether is 1 (1) - (10) to 1 (1) - (10).

Furthermore, the concentration of the ammonia water is 28-30%, and the addition amount is 10-200 mL.

In step S20, the addition amount of the nonylphenol polyoxyethylene ether solution is 2 to 10mL, the concentration is 10 to 100mmol/L, the addition amount of cyclohexane is 20 to 50mL, and the concentration is more than or equal to 99.5%.

Further, in step S40, the molar concentration of the tetraethyl silicate solution is 4 to 10mol/L, the molar concentration of the N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution is 3 to 5mol/L, the total addition amount of the N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution is 0.5 to 20ml, and the volume ratio of the N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution added in the two steps is 1 to 1.

The invention also provides a coating additive prepared by the preparation method. The paint additive is a silver-loaded molecular sieve, has good antibacterial and antiviral properties, is not easy to generate drug resistance, has good compatibility and stability with the paint, and can be used for preparing antibacterial and antiviral paint.

The invention also aims to provide an application of the coating additive prepared by the preparation method on a coating. The coating comprises water-based coating, solvent-based coating and inorganic coating.

The invention has the beneficial effects that: the invention utilizes a method of reverse microemulsion to synthesize a mesoporous silica molecular sieve capable of coating silver ions by rapid hydrolysis and condensation of silane on an aminosilane modified surface, the silver ions are introduced into a pore structure of the molecular sieve while the mesoporous silica molecular sieve is synthesized, and the silver ions can be prevented from precipitating by utilizing the coordination effect of a coordination agent on the silver ions, so that the silver ions are slowly released, the antibacterial and antiviral durability is improved.

Drawings

FIG. 1 is a small angle X-ray scattering plot for example 1, comparative example 2, and comparative example 7.

Fig. 2 is an X-ray diffraction pattern of example 1, comparative example 2, and comparative example 7.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.

(1) Preparing 14.7mmol/L silver nitrate water solution.

(2) Adding 25mL silver nitrate aqueous solution into 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L), and simultaneously adding into 200mL mixed solution composed of serinol and tromethamine, wherein the quantity ratio of raw material substances is n (serinol): n (tromethamine): n (nonylphenol polyoxyethylene ether Type NP-7) = 2.

(3) Adding 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L) into 20mL cyclohexane, and mixing uniformly.

(4) And (4) mixing the solutions in the step (2) and the step (3), adding 25mL of 28-30% ammonia water and 25mL deionized water, and vigorously stirring and keeping for a period of time.

(5) Mixing 3.25mL of 4mol/L tetraethyl silicate solution and 0.75mL of 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture into the mixed solution obtained in the step (4) for 2 times after mixing, adding 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution once every half hour, adding 100 mu L of the solution every time, and stirring at room temperature for 48 hours after continuously adding the solution for 5 times;

(6) Heating and stirring for 8 hours at 120 ℃ in a nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and carrying out vacuum drying for 18 hours to obtain the coating additive.

Example 2

(1) Preparing 14.7mmol/L silver nitrate water solution.

(2) Adding 25mL silver nitrate aqueous solution into 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L), and simultaneously adding into 200mL mixed solution composed of serinol and tromethamine, wherein the quantity ratio of raw materials is n (serinol): n (tromethamine): n (nonylphenol polyoxyethylene ether Type NP-7) = 4.

(3) 4mL nonylphenol polyoxyethylene ether solution (15 mmol/L) is added into 40mL cyclohexane and mixed evenly.

(4) And (3) mixing the solutions in the step (2) and the step (3), adding 25mL of 28-30% ammonia water and 25mL deionized water, and violently stirring and keeping for a period of time.

(5) Mixing 3.25mL of a 4mol/L tetraethyl silicate solution and 0.75mL of a 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture to the mixed solution obtained in the step (4), repeating the step for 5 times, adding 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution every half hour, adding 100. Mu.L of the solution every time, and stirring the solution at room temperature for 48 hours after continuously adding the solution for 3 times;

(6) Heating and stirring for 8 hours at 120 ℃ in the nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and drying for 18 hours in vacuum to obtain the silver-loaded molecular sieve antibacterial and antiviral agent.

Example 3

(1) Preparing 29.4mmol/L silver nitrate water solution.

(2) Adding 25mL silver nitrate aqueous solution into 2mL nonylphenol polyoxyethylene ether solution (30 mmol/L), and simultaneously adding into 200mL mixed solution composed of serinol and tromethamine, wherein the quantity ratio of raw material substances is n (serinol): n (tromethamine): n (nonylphenol polyoxyethylene ether Type NP-10) = 4.

(3) 4mL nonylphenol polyoxyethylene ether solution (30 mmol/L) is added into 40mL cyclohexane and mixed evenly.

(4) And (3) mixing the solutions in the step (2) and the step (3), adding 50mL of 28-30% ammonia water and 25mL deionized water, and violently stirring and keeping for a period of time.

(5) Mixing 3.25mL of 8mol/L tetraethyl silicate solution and 0.75mL of 5mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture to the mixed solution in the step (4) after mixing, repeating the step for 5 times, adding 5mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution every half hour, adding 100 mu L of the solution every time, continuously adding for 5 times, and stirring at room temperature for 48 hours;

(6) Heating and stirring for 8 hours at 120 ℃ in the nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and drying for 18 hours in vacuum to obtain the silver-loaded molecular sieve antibacterial and antiviral agent.

Comparative example 1

(1) 25mL of a 0.0147mol/L aqueous silver nitrate solution was prepared.

(2) Mixing 3.25mL of 4mol/L tetraethyl silicate solution and 0.75mL of 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture into the mixed solution obtained in the step (1) in 2 steps after mixing, adding 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution every half hour, adding 100 mu L of the solution every time, and stirring at room temperature for 48 hours after continuously adding the solution for 5 times;

(3) Heating and stirring for 8 hours at 120 ℃ in the nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and drying for 18 hours in vacuum to obtain the silver-loaded molecular sieve antibacterial and antiviral agent.

Comparative example 2

(1) Preparing 5mL of 1 mol/L sodium metaaluminate solution.

(2) Adding 3.192 g sodium silicate to 15mL of 0.5 mol/L sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the solution in the step (1), generating white sol, transferring the mixture into a reaction kettle, crystallizing for 8 hours at 90 ℃, centrifuging and washing with deionized water for three times, vacuum drying for 8 hours at 105 ℃ to obtain a silicon dioxide molecular sieve, and collecting the silicon dioxide molecular sieve for later use.

(3) Preparing 25mL of 0.0147mol/L silver nitrate aqueous solution, adding the 2 g silicon dioxide molecular sieve obtained in the step (1) under stirring at 35 ℃, adjusting the pH to 7 by using 0.1 mol/L nitric acid and 0.5 mol/L sodium hydroxide solution, after 2 hours of ion exchange, stopping stirring, centrifuging and washing by using deionized water for three times, and putting the ion-exchanged molecular sieve into an oven to carry out vacuum drying at 105 ℃ for 18 hours to obtain the silver-loaded molecular sieve.

Comparative example 3

(1) Silver nitrate aqueous solution with a molar concentration of 0.0147mol/L is placed.

(2) Adding 25mL silver nitrate aqueous solution into 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L), and simultaneously adding into 200mL mixed solution composed of serinol and tromethamine, wherein the quantity ratio of raw material substances is n (serinol): n (tromethamine): n (nonylphenol polyoxyethylene ether Type NP-7) = 2.

(3) Adding 2mL nonylphenol polyoxyethylene ether solution into 20mL cyclohexane, and mixing uniformly.

(4) And (3) mixing the solutions in the step (2) and the step (3), adding 25mL of 28-30% ammonia water and 25mL deionized water, and violently stirring and keeping for a period of time.

(5) Adding 4mL of 4mol/L tetraethyl silicate solution into the mixed solution obtained in the step (4), repeating the step for 2 times, and stirring at room temperature for 48 hours;

(6) Heating and stirring for 8 hours at 120 ℃ in the nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and drying for 18 hours in vacuum to obtain the silver-loaded molecular sieve antibacterial and antiviral agent.

Comparative example 4

(1) An aqueous silver nitrate solution having a molar concentration of 0.0147mol/L was prepared.

(2) Adding 25mL silver nitrate aqueous solution into 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L), and simultaneously adding into 200mL mixed solution composed of serinol and tromethamine, wherein the quantity ratio of raw material substances is n (serinol): n (tromethamine): n (nonylphenol polyoxyethylene ether Type NP-7) = 2.

(3) Adding 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L) into 20mL cyclohexane, and mixing uniformly.

(4) And (3) mixing the solutions in the step (2) and the step (3), adding 25mL of 28-30% ammonia water and 25mL deionized water, and violently stirring and keeping for a period of time.

(5) Mixing 3.25mL of 4mol/L tetraethyl silicate solution and 0.80 mL of 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture into the mixed solution obtained in the step (4), and stirring at room temperature for 48 hours;

(6) Heating and stirring for 8 hours at 120 ℃ in the nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and drying for 18 hours in vacuum to obtain the silver-loaded molecular sieve antibacterial and antiviral agent.

Comparative example 5

(1) Silver nitrate aqueous solution with a molar concentration of 0.0147mol/L was prepared.

(2) Adding 25mL silver nitrate aqueous solution into 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L), and simultaneously adding into 200mL mixed solution composed of serinol and tromethamine, wherein the quantity ratio of raw material substances is n (serinol): n (tromethamine): n (nonylphenol polyoxyethylene ether Type NP-7) = 2.

(3) Adding 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L) into 20mL cyclohexane, and mixing uniformly.

(4) And (3) mixing the solutions in the step (2) and the step (3), adding 25mL of 28-30% ammonia water and 25mL deionized water, and violently stirring and keeping for a period of time.

(5) Mixing 3.25mL of a 4mol/L tetraethyl silicate solution and 0.75mL of a 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture to the mixed solution obtained in the step (4), adding 500 μ L of a 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution at a time, and stirring at room temperature for 48 hours;

(6) Heating and stirring for 8 hours at 120 ℃ in the nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and drying for 18 hours in vacuum to obtain the silver-loaded molecular sieve antibacterial and antiviral agent.

Comparative example 6

(1) Silver nitrate aqueous solution with a molar concentration of 0.0147mol/L was prepared.

(2) Adding 25mL silver nitrate aqueous solution into 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L), and simultaneously adding into 200mL mixed solution composed of serinol and tromethamine, wherein the quantity ratio of raw material substances is n (serinol): n (tromethamine): n (nonylphenol polyoxyethylene ether Type NP-7) = 2.

(3) Adding 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L) into 20mL cyclohexane, and mixing uniformly.

(4) And (4) mixing the solutions in the step (2) and the step (3), adding 25mL of 28-30% ammonia water and 25mL deionized water, and vigorously stirring and keeping for a period of time.

(5) Mixing 3.25mL of a 4mol/L tetraethyl silicate solution and 0.75mL of a 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture to the mixed solution obtained in the step (4), repeating the step for 2 times, and stirring at room temperature for 48 hours;

(6) Heating and stirring for 8 hours at 120 ℃ in the nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and drying for 18 hours in vacuum to obtain the silver-loaded molecular sieve antibacterial and antiviral agent.

Comparative example 7

(1) Silver nitrate aqueous solution with a molar concentration of 0.0147mol/L was prepared.

(2) Step (1) was added to 34 mL of a Span80-Tween 60-cyclohexane solution, where n (Span 80): n (Tween 60): n (cyclohexane) =2, and the mixture is uniformly mixed and then 1 mol/L of HCl solution is dripped until the system becomes transparent and clear.

(3) Mixing 25mL of a 4mol/L tetraethyl silicate solution and 0.75mL of a 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture into the mixed solution obtained in the step (2) after mixing, repeating the step for 2 times, adding the 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution once every half hour, adding 100 mu L of the solution every time, and stirring at room temperature for 48 hours after continuously adding the solution for 5 times;

(4) Heating and stirring for 8 hours at 120 ℃ in the nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and drying for 18 hours in vacuum to obtain the silver-loaded molecular sieve antibacterial and antiviral agent.

Comparative example 8

(1) Silver nitrate aqueous solution with a molar concentration of 0.0147mol/L was prepared.

(2) Adding 25mL silver nitrate aqueous solution into 150 mL mixed solution composed of serinol and tromethamine, wherein the amount ratio of raw material substances is n (serinol): n (tromethamine) =1:2.

(3) Adding 2mL nonylphenol polyoxyethylene ether solution (15 mmol/L) into 20mL cyclohexane, and mixing uniformly.

(4) And (3) mixing the solutions in the step (2) and the step (3), adding 25mL of 28-30% ammonia water and 25mL deionized water, and violently stirring and keeping for a period of time.

(5) Mixing 3.25mL of 4mol/L tetraethyl silicate solution and 0.75mL of 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture into the mixed solution obtained in the step (4) in 2 steps after mixing, adding 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution once every half hour, adding 100 mu L of the solution every time, and stirring at room temperature for 48 hours after continuously adding for 5 times;

(6) Heating and stirring for 8 hours at 120 ℃ in the nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and carrying out vacuum drying for 18 hours to obtain the coating additive.

The paint additives prepared in the working examples 1~3 and the comparative example 1~8 are tested for the antibacterial and antiviral effects in paints, the addition amount of the paint additive is 0.6%, the antibacterial test is referred to the GB/T21866-2008 antibacterial paint (paint film) antibacterial property test method and antibacterial effect test standard, and the antiviral test is referred to the T/CNCIA 03002-2020 paint (paint film) antiviral property test method, and the results are shown in Table 1.

TABLE 1 coating antibacterial and antiviral test results

XRD examination of some of the coating additives prepared in the examples and comparative examples gave small angle X-ray scattering patterns and X-ray diffraction patterns as shown in FIGS. 1 and 2.

As can be seen from the small-angle X-ray scattering diagram in FIG. 1, the mesoporous silica supports were successfully synthesized in example 1, comparative example 1 and comparative example 7, but the diffraction peak intensity of the curve is weaker in the case of not adopting the reverse microemulsion method and nonylphenol polyoxyethylene ether, which indicates that the silane can not be hydrolyzed into the silica support under the condition change in the synthesis process. The silver-loaded molecular sieve prepared by the conventional method in the comparative example 2 does not form a silica carrier with a mesoporous structure.

The curve of example 1 in the X-ray diffraction diagram of FIG. 2 is 21.7 DEG 2 theta,Diffraction peaks appear at 24.4 °, 28.2 °, 29.5 °, 31.8 °, 32.7 °, 35.5 °, 36.4 °, 39.1 °, 40.1 °, 43.5 °, 46.4 °, 47.9 °, 48.5 °, 54.0 °, 54.8 °, 58.3 °, and 61.8 °, which is similar to AgNO in the figure ₃ Consistent with JCPDS card 06-0363, demonstrates the success of example 1 in synthesizing silver-loaded molecular sieve antibacterial antiviral agents, i.e., coating additives, in which the silver is present in the form of silver ions.

Comparative example 1 shows diffraction peaks at 32.9 ° and 38.3 ° 2 θ, indicating the presence of silver oxide in the sample, and silver ions are oxidized during the reaction without combining the silver ion complex into a water-in-oil reverse microemulsion system, and the final product also appears as a black powder.

The diffraction peaks of the curves of comparative example 2 and comparative example 7 show that the material has a lower silver ion content than example 1, indicating that the coating additive is prepared using conventional methods and that the binding of silver ions to the molecular sieve is hindered, resulting in a material with a lower silver content, without the use of nonylphenol polyoxyethylene ether as the reverse microemulsion component.

The above examples are only intended to illustrate the detailed process of the present invention, and the present invention is not limited to the above detailed process, i.e., it is not intended that the present invention necessarily depends on the above detailed process for its implementation. It is understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (5)

1. A preparation method of a coating additive with antibacterial and antiviral functions is characterized by comprising the following steps:

(1) Preparing a silver nitrate aqueous solution with a concentration of 14.7mmol/L mol;

(2) Adding 25mL of silver nitrate aqueous solution into 2mL of 15mmol/L nonylphenol polyoxyethylene ether solution, and simultaneously adding into 200mL of mixed solution composed of serinol and tromethamine, wherein the amount ratio of raw materials is n (serinol): n (tromethamine): n (nonylphenol polyoxyethylene ether Type NP-7) = 2;

(3) Adding 2mL of nonylphenol polyoxyethylene ether solution of 15mmol/L into 20mL of cyclohexane, and uniformly mixing;

(4) Mixing the solutions in the steps (2) and (3), adding 25mL of 28-30% ammonia water and 25mL of deionized water, and violently stirring and keeping for a period of time;

(5) Mixing 3.25mL4mol/L tetraethyl silicate solution and 0.75mL 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture into the mixed solution obtained in the step (4) by 2 times after mixing, adding 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution once every half hour, adding 100 mu L of the solution every time, and stirring at room temperature for 48 hours after continuously adding the solution for 5 times;

(6) Heating and stirring for 8 hours at 120 ℃ in a nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and carrying out vacuum drying for 18 hours to obtain the coating additive.

2. A preparation method of a coating additive with antibacterial and antiviral functions is characterized by comprising the following steps:

(1) Preparing a silver nitrate aqueous solution with the concentration of 14.7mmol/L mol;

(2) Adding 25mL of silver nitrate aqueous solution into 2mL15mmol/L nonylphenol polyoxyethylene ether solution, and simultaneously adding into 200mL of mixed solution composed of serinol and tromethamine, wherein the mass ratio of raw materials is n (serinol): n (tromethamine): n (nonylphenol polyoxyethylene ether Type NP-7) = 4;

(3) Adding 4mL of 15mmol/L nonylphenol polyoxyethylene ether solution into 40mL of cyclohexane, and uniformly mixing;

(4) Mixing the solutions in the steps (2) and (3), adding 25mL of 28-30% ammonia water and 25mL of deionized water, and violently stirring and keeping for a period of time;

(5) Mixing 3.25mL of a 4mol/L tetraethyl silicate solution and 0.75mL of a 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution, adding the mixture after mixing to the mixed solution in the step (4), repeating the step for 5 times, adding 3mol/L N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution every half hour, adding 100 mu L of the solution every time, and stirring at room temperature for 48 hours after continuously adding for 3 times;

(6) Heating and stirring for 8 hours at 120 ℃ in a nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and carrying out vacuum drying for 18 hours to obtain the coating additive.

3. A preparation method of a coating additive with antibacterial and antiviral functions is characterized by comprising the following steps:

(1) Preparing a silver nitrate aqueous solution with a concentration of 29.4mmol/L mol;

(2) Adding 25mL of silver nitrate aqueous solution into 2mL30 mmol/L nonylphenol polyoxyethylene ether solution, and simultaneously adding into 200mL of mixed solution composed of serinol and tromethamine, wherein the mass ratio of raw materials is n (serinol): n (tromethamine): n (nonylphenol polyoxyethylene ether Type NP-10) = 4;

(3) Adding 4mL of 30 mmol/L nonylphenol polyoxyethylene ether solution into 40mL of cyclohexane, and uniformly mixing;

(4) Mixing the solutions in the steps (2) and (3), adding 50mL of 28-30% ammonia water and 25mL of deionized water, and violently stirring and keeping for a period of time;

(5) Mixing 3.25mL of tetraethyl silicate solution of 8mol/L and 0.75mL of N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution of 5mol/L, adding the mixture to the mixed solution obtained in the step (4), repeating the step for 5 times, adding 5mol/L of N- [3- (trimethoxysilyl) propyl ] ethylenediamine solution every half hour, adding 100. Mu.L of each solution, continuously adding for 5 times, and stirring at room temperature for 48 hours;

(6) Heating and stirring for 8 hours at 120 ℃ in a nitrogen atmosphere, taking out solids, centrifugally washing for 3 times by using ethanol and acetone to remove residual organic matters, centrifugally washing by using deionized water, and carrying out vacuum drying for 18 hours to obtain the coating additive.

4. A paint additive, characterized in that it is obtained by the process according to any one of claims 1 to 3.

5. Use of a coating additive prepared by the process of any one of claims 1 to 3 in a coating.

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