CN113662008A - Preparation method of normal-temperature curing type micro-nano zinc long-acting antibacterial mildew inhibitor - Google Patents
Preparation method of normal-temperature curing type micro-nano zinc long-acting antibacterial mildew inhibitor Download PDFInfo
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Abstract
The invention discloses a preparation method of a normal-temperature curing type micro-nano zinc long-acting antibacterial mildew preventive, which comprises the following steps: preparing zinc particles with the particle size of 10 nm-600 nm by using a micro-emulsion method according to a proportion; transferring the prepared nano zinc particles to the next reaction kettle, and preparing a micro-nano zinc solution by cavitation erosion; adding an initiator and a modifier into the other reaction kettle, heating and stirring to obtain a polymer A; adding acrylate into the polymer A, and stirring to react to obtain a polymer B; dispersing the micro-nano zinc solution in a dispersing agent A to prepare a dispersion liquid A; adding the dispersion liquid A into the polymer B, and fully stirring to prepare the normal-temperature curing micro-nano zinc long-acting antibacterial mildew inhibitor; the antibacterial and antifungal agent can form a film at normal temperature, has the characteristics of long-acting antibacterial property, mildew resistance, washing resistance and wide applicability, and is safe, nontoxic, environment-friendly and free of drug resistance.
Description
Technical Field
The invention relates to the technical field of antibacterial mildew inhibitors, and particularly relates to a preparation method of a normal-temperature curing type micro-nano zinc long-acting antibacterial mildew inhibitor.
Background
Most of the traditional disinfectants are short-acting antibacterial agents which are easy to volatilize and decompose, and the antibacterial effect of the traditional disinfectants is rapidly reduced, and the traditional disinfectants such as alcohol, hydrogen peroxide and the like can meet daily disinfection by frequent use for many times. The investigation result of disease control on the current situation of microbial contamination on the surfaces of objects in more than 200 hospitals nationwide in 2014 shows that the total number of bacterial colonies is remarkably increased after 8 hours after the object surface is sterilized. Meanwhile, the disinfectant cannot avoid the defects of corrosivity, irritation and the like in the use process.
Public environment and living environment are conventional ways for transmitting pathogenic microorganisms, people are in daily contact with various public facilities such as tables and chairs, door handles, handrail, home furnishing, toys and the like, various microorganisms which cannot be seen by naked eyes exist on the surfaces of the public facilities, and a plurality of pathogenic bacteria also exist on the surfaces of the public facilities. With the attention of people on health problems, attention is paid to a long-acting antibacterial treatment technology on the surfaces of various objects.
At present, products with long-acting antibacterial function are mainly concentrated in products such as coatings, textiles, plastics, metal products and the like.
Disclosure of Invention
Aiming at the defects, the invention provides the long-acting antibacterial mildew preventive capable of forming a film at normal temperature, which not only has the characteristics of long-acting antibacterial property, mildew resistance, washing resistance and wide applicability, but also is safe, non-toxic, environment-friendly and free of drug resistance.
According to the invention, by controlling the reaction conditions, the micro-nano zinc with the particle size of 10nm to 600nm is prepared, and cavitation erosion phenomenon is applied to form an erosion pit on the particle surface of the zinc particle so as to improve the effect of rapidly sterilizing and inactivating viruses.
It is accepted at home and abroad that when the average diameter phi of the nanoparticles is less than 100nm, the particles are called nanoparticles. The diameter of the prepared zinc particles is between nanometer and micrometer, so the micro-nano zinc is called micrometer nano zinc and is called micro-nano zinc for short.
In order to achieve the purpose, the invention provides the following specific technical scheme:
a preparation method of a normal-temperature curing type micro-nano zinc long-acting antibacterial mildew preventive comprises the following steps:
step 1: preparing a zinc particle solution by using a micro-emulsion method, wherein the particle size of zinc particles is 10-600 nm;
step 2: transferring the prepared zinc particle solution to the next reaction kettle, and preparing a micro-nano zinc solution by utilizing a cavitation phenomenon;
and step 3: mixing 25-55 parts by mass of an initiator and 10-25 parts by mass of a modifier, and reacting to obtain a polymer A;
and 4, step 4: adding 10-15 parts by mass of acrylic ester into the polymer A obtained in the step (3), stirring and mixing, and reacting to obtain a polymer B;
and 5: adding 2-6 parts by mass of the micro-nano zinc solution prepared in the step 2 into 8.5-41.5 parts by mass of the dispersing agent A, and stirring and dispersing to obtain a dispersion liquid A;
step 6: and (4) adding the dispersion liquid A into the polymer B prepared in the step (4), and fully stirring uniformly to prepare the normal-temperature curing micro-nano zinc long-acting antibacterial mildew preventive.
Further, the step 1 also comprises a step 1.1: dissolving a surfactant in an organic solvent, mixing with a cosurfactant and deionized water, and stirring to prepare a WPO (waterborne polyurethane emulsion) reverse microemulsion system; step 1.2: respectively adding a zinc salt aqueous solution with the concentration of 400-600 g/L and a hydrazine hydrate solution into the WPO reverse-phase microemulsion system, stirring and mixing, reacting at the temperature of 40-80 ℃ and the stirring speed of 2000-5000 rpm for 5-8 h to obtain a zinc particle solution with the particle size of 10-600 nm.
Further, in the step 1.1, the volume ratio of the total volume of the surfactant, the cosurfactant and the organic solvent to the deionized water is 1-4: 1, and the volume ratio of the surfactant, the cosurfactant and the organic solvent is 1-5: 1: 2-4; the volume ratio of the zinc salt aqueous solution to the hydrazine hydrate solution in the step 1.2 is 1:1, and the volume ratio of the hydrazine hydrate solution to the WPO reverse microemulsion system is 1: 3.5-4.
Further, in the step 1.1, the surfactant is a nonionic surfactant, and the organic solvent is one or more of alkane and cycloalkane; the cosurfactant is fatty alcohol; the zinc salt in the step 1.2 is one or more of zinc sulfate, zinc nitrate, zinc citrate and zinc gluconate.
Further, the nonionic surfactant is one or more of polyoxyethylene vinyl nonylphenyl ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether and high-carbon fatty polyoxyethylene ether; the organic solvent is cyclohexane; the cosurfactant is one or more of isoamyl alcohol, n-heptanol, n-octanol, n-nonanol, n-decanol and cetyl alcohol.
Further, the step 2 further comprises:
step 2.1: transferring the zinc particle solution prepared in the step 1 to a next reaction kettle, stirring at 60 ℃, wherein the stirring speed is 2000-5000 rpm, and introducing high-speed air flow to form a cavitation phenomenon;
step 2.2: reacting for 5 hours to prepare the micro-nano zinc solution.
Further, the reaction temperature in the step 3 is 70-95 ℃; preferably, the reaction temperature is preferably 80 to 90 ℃, and most preferably 85 ℃.
Further, the initiator in the step 3 is one or more of diphenol propane epoxy resin, butylene epoxy resin and cyclopentadiene epoxy resin; the modifier in the step 3 is one or more of pentaerythritol, glycerol, xylitol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, diethyl toluene diamine and sorbitol.
The mass part of the initiator in the step 3 is preferably 30-50 parts, and most preferably 40 parts.
The mass part of the modifier in the step 3 is preferably 14-21 parts, and most preferably 17.5 parts.
Further, the rotating speed of stirring in the step 4 is 900-1200 rpm, and the reaction time is 2-6 hours.
Preferably, the stirring speed in the step 4 is 950-1050 rpm, and the reaction time is 3-5 hours; most preferably, the rotation speed of the stirring in the step 4 is 1000 rpm, and the reaction time is 4 hours.
Further, the acrylate in the step 4 is one or more of methyl acrylate, ethyl acrylate, 2-methyl methacrylate, 2-ethyl methacrylate, hydroxyethyl acrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate and hydroxymethyl methacrylate.
The mass part of the acrylate in the step 4 is preferably 11.5-14.5 parts, and most preferably 12.5 parts.
Further, the dispersant A in the step 5 is one or more of ethylene glycol, ethanol, butanol and water.
The mass part of the dispersing agent A in the step 5 is preferably 10-30 parts, and most preferably 26 parts; the mass part of the micro-nano zinc solution is preferably 2-6 parts, more preferably 3-5 parts, and most preferably 4 parts.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the invention, the micro-emulsion method is utilized to prepare the micro-nano zinc particle solution, the preparation device has the advantages of simple structure, easily available apparatus, low cost, easy operation in solution preparation, controllable zinc particles, difficult agglomeration and the like; the surface of the micro-nano zinc forms irregular spikes, bacteria and mould can be quickly killed by the attraction of coulomb force and the spikes, so that the bacteria and mould can not be continuously propagated or transferred, and the prepared micro-nano zinc particle solution is non-toxic, harmless, tasteless and non-irritant, can replace most of disinfection products, is beneficial to environmental protection, improves the healthy living level, and achieves the effects of really, durably, effectively, stably, efficiently, environmentally and tasteless sterilization.
The antibacterial agent generally needs to be effectively contacted with bacteria and the like in a liquid state so as to play an antibacterial role, but continuous antibacterial action cannot be carried out, the antibacterial liquid is solidified into a film, and zinc particles contained on the surface of the film are contacted with the bacteria and the like so as to be antibacterial and not lost, so that the aim of continuous antibacterial action is fulfilled; the epoxy resin is modified by the polyhydric alcohol, so that the flexibility of the epoxy resin is improved, the viscosity is reduced, the acrylic ester is introduced, the acrylic ester has good compatibility with the modified epoxy resin, and the thermal oxidation resistance of the liquid is improved; meanwhile, the zinc plays a role of a drier, so that the antibacterial mildew preventive is easier to be solidified into a film at room temperature in the spraying use process, the washing resistance of the antibacterial mildew preventive is improved, the loss of antibacterial components is prevented, and the long-acting antibacterial performance is kept.
The modifier and the acrylate used in the invention can improve the stability of the micro-nano zinc solution, ensure the uniform stability of the antibacterial mildew preventive before spraying, and avoid layering and agglomeration.
The antibacterial mildew inhibitor provided by the invention has excellent antibacterial mildew-proof effect, the antibacterial performance is more than or equal to 99.00%, and the mildew-proof grade is 0 (no mildew growth); the long-acting antibacterial mildew preventive has an excellent long-acting antibacterial effect, and meanwhile, after the long-acting antibacterial mildew preventive is smeared on a plastic plate and an aluminum plate and dried to form a film, the film is wiped by clear water for 30 days and then is detected, and the sterilization rate is more than or equal to 99.00 percent; the antibacterial mildew inhibitor provided by the invention is safe and nontoxic, is environment-friendly and human-friendly, can be applied to various occasions, and is environment-friendly and pollution-free.
Drawings
FIG. 1 is a micro-structure diagram of micro-nano zinc before cavitation erosion;
FIG. 2 is a micro-structure diagram of micro-nano zinc with etching pits obtained by cavitation in the invention;
FIG. 3 is a particle size distribution diagram of the micro-nano zinc of the invention;
FIG. 4 is a morphological diagram of a cultured colony after the micro-nano zinc solution acts for 20s in example 2 of the invention;
FIG. 5 is a morphological diagram of a cultured colony after a micro-nano zinc solution acts for 30s in example 2 of the invention;
FIG. 6 is a morphological diagram of a cultured colony after a micro-nano zinc solution acts for 60s in example 2 of the invention;
fig. 7 is a long-acting antibacterial effect diagram of the micro-nano zinc long-acting antibacterial mildew preventive.
Detailed Description
The present invention is described in detail below with reference to the drawings and examples, but the present invention is not limited thereto.
Example 1
Preparing micro-nano zinc:
step 1.1: dissolving 50mL of nonylphenol polyoxyethylene ether and 30mL of n-octanol in 120mL of cyclohexane, and stirring with 20mL of isoamyl alcohol and 200mL of deionized water to prepare a WPO (waterborne polyurethane emulsion) reverse microemulsion system;
step 1.2: adding 1000mL of mixed solution of zinc citrate and zinc nitrate with the concentration of 450g/L and 1000mL of hydrazine hydrate solution into 3600mL of WPO reverse microemulsion for mixing, and reacting for 6.5h at 65 ℃ and the rotating speed of 4600rpm to prepare zinc particle solution with the particle size of 10-600 nm;
step 2.1: transferring the prepared zinc particle solution into the next reaction kettle, stirring at 60 ℃, 4600rpm, and introducing high-speed air flow to form a cavitation phenomenon;
step 2.2: the reaction time is 5 hours, and a micro-nano zinc solution is prepared;
a TEM image of the prepared zinc particles is shown in FIG. 1, and a TEM image of the prepared micro-nano zinc is shown in FIG. 2.
As shown in fig. 3, the microemulsion method is used to prepare zinc with the particle size between micron and nanometer, and the reaction conditions are controlled to prepare zinc particles with the particle size: phi is more than 10nm and less than 600 nm;
preferred results are: the zinc particles with the particle size of 100nm < phi < 600nm account for 30 percent of the total number.
Example 2
The micro-nano zinc solution prepared in the example 1 is prepared into a micro-nano zinc aqueous solution with the concentration of 1000mg/kg, and then the micro-nano zinc aqueous solution is sequentially diluted into a solution with the concentration of: the micro-nano zinc aqueous solutions with the concentrations of 1000mg/kg, 800mg/kg, 500mg/kg, 400mg/kg and 300mg/kg are marked as group 5, group 4, group 3, group 2 and group 1 in sequence.
The sterilization rate of the micro-nano zinc aqueous solution is measured according to a suspension quantitative method of 'sterilization technical specification', the test strains are escherichia coli, staphylococcus aureus, candida albicans and pseudomonas aeruginosa, and the test time is 20s, 30s and 60s respectively; the test results are shown in table 1, the morphologies of the cultured colonies after the micro-nano zinc aqueous solutions with different concentrations in the groups 1 to 5 act on escherichia coli, staphylococcus aureus, candida albicans and pseudomonas aeruginosa for 20s are shown in fig. 4, the morphologies of the cultured colonies after the micro-nano zinc aqueous solutions act on escherichia coli, staphylococcus aureus, candida albicans and pseudomonas aeruginosa for 30s are shown in fig. 5, and the morphologies of the cultured colonies after the micro-nano zinc aqueous solutions act on escherichia coli, staphylococcus aureus, candida albicans and pseudomonas aeruginosa for 60s are shown in fig. 6.
According to the technical specification of disinfection, the virus inactivation rate of the micro-nano zinc aqueous solution is determined, the tested viruses are poliovirus, influenza A virus H1N1, enterovirus and avian influenza virus H5N1, and the test time is 10s, 20s and 30s respectively; the test results are shown in table 2.
Preparing the micro-nano zinc prepared in the embodiment 1 into an aqueous solution with the concentration of 1000mg/kg, diluting the micro-nano zinc aqueous solution by 10000 times to obtain a micro-nano zinc aqueous solution with the concentration of 100 mug/kg, and taking 5 parallel samples to mark as: group 1, group 2, group 3, group 4 and group 5, groups 1 to 5 respectively with a concentration of 106TCID50Mixing pseudorabies virus and coronavirus (PEDV) in a contact manner for 30min, and measuring the virus inactivation rate; the test results are shown in table 3.
TABLE 1 Sterilization effect of micro-nano zinc solution under different time
TABLE 2 Virus inactivating effect of micro-nano zinc solution at different time
TABLE 3 Virus inactivating effect of micro-nano zinc solution
According to the experimental data, the micro-nano zinc solution prepared by the method can realize the effect of rapid sterilization.
Example 3
A preparation method of a normal-temperature curing type micro-nano zinc long-acting antibacterial mildew preventive comprises the following steps:
step 1.1: dissolving 50mL of nonylphenol polyoxyethylene ether and 30mL of n-octanol in 120mL of cyclohexane, and stirring with 20mL of isoamyl alcohol and 200mL of deionized water to prepare a WPO (waterborne polyurethane emulsion) reverse microemulsion system;
step 1.2: adding 1000mL of mixed solution of zinc citrate and zinc nitrate with the concentration of 450g/L and 1000mL of hydrazine hydrate solution into 3600mL of WPO reverse microemulsion for mixing, and reacting for 6.5h at 65 ℃ and the rotating speed of 4600rpm to prepare zinc particle solution with the particle size of 10-600 nm;
step 2.1: transferring the prepared zinc particle solution into the next reaction kettle, stirring at 60 ℃, 4600rpm, and introducing high-speed air flow to form a cavitation phenomenon;
step 2.2: the reaction time is 5 hours, and a micro-nano zinc solution is prepared;
and step 3: adding 25 parts by mass of diphenol propane epoxy resin and 30 parts by mass of pentaerythritol into a reaction kettle, heating to 70 ℃, and uniformly stirring to obtain a polymer A;
and 4, step 4: adding 10 parts by mass of methyl acrylate into the polymer A obtained in the step (3), and stirring and reacting for 2 hours at the rotating speed of 1200 rpm to obtain a polymer B;
and 5: adding 2 parts by mass of micro-nano zinc solution into 33 parts by mass of ethylene glycol, and stirring and dispersing to obtain a dispersion liquid A;
step 6: and (4) adding the dispersion liquid A into the polymer B prepared in the step (4), and fully stirring uniformly to prepare the normal-temperature curing micro-nano zinc long-acting antibacterial mildew preventive.
Example 4
A preparation method of a normal-temperature curing type micro-nano zinc long-acting antibacterial mildew preventive comprises the following steps:
step 1.1: dissolving 50mL of nonylphenol polyoxyethylene ether and 30mL of n-octanol in 120mL of cyclohexane, and stirring with 20mL of isoamyl alcohol and 200mL of deionized water to prepare a WPO (waterborne polyurethane emulsion) reverse microemulsion system;
step 1.2: adding 1000mL of mixed solution of zinc citrate and zinc nitrate with the concentration of 450g/L and 1000mL of hydrazine hydrate solution into 3600mL of WPO reverse microemulsion for mixing, and reacting for 6.5h at 65 ℃ and the rotating speed of 4600rpm to prepare zinc particle solution with the particle size of 10-600 nm;
step 2.1: transferring the prepared zinc particle solution into the next reaction kettle, stirring at 60 ℃, 4600rpm, and introducing high-speed air flow to form a cavitation phenomenon;
step 2.2: the reaction time is 5 hours, and a micro-nano zinc solution is prepared;
and step 3: adding 45 parts by mass of butene epoxy resin and 25 parts by mass of diethylene glycol into a reaction kettle, heating to 90 ℃, and uniformly stirring to obtain a polymer A;
and 4, step 4: adding 14.5 parts by mass of hydroxyethyl acrylate into the polymer A obtained in the step (3), and stirring and reacting at the rotating speed of 900 revolutions per minute for 5 hours to obtain a polymer B;
and 5: adding 5 parts by mass of micro-nano zinc solution into 10.5 parts by mass of water, and stirring and dispersing to obtain dispersion liquid A;
step 6: and (4) adding the dispersion liquid A into the polymer B prepared in the step (4), and fully stirring uniformly to prepare the normal-temperature curing micro-nano zinc long-acting antibacterial mildew preventive.
Example 5
A preparation method of a normal-temperature curing type micro-nano zinc long-acting antibacterial mildew preventive comprises the following steps:
step 1.1: dissolving 50mL of nonylphenol polyoxyethylene ether and 30mL of n-octanol in 120mL of cyclohexane, and stirring with 20mL of isoamyl alcohol and 200mL of deionized water to prepare a WPO (waterborne polyurethane emulsion) reverse microemulsion system;
step 1.2: adding 1000mL of mixed solution of zinc citrate and zinc nitrate with the concentration of 450g/L and 1000mL of hydrazine hydrate solution into 3600mL of WPO reverse microemulsion for mixing, and reacting for 6.5h at 65 ℃ and the rotating speed of 4600rpm to prepare zinc particle solution with the particle size of 10-600 nm;
step 2.1: transferring the prepared zinc particle solution into the next reaction kettle, stirring at 60 ℃, 4600rpm, and introducing high-speed air flow to form a cavitation phenomenon;
step 2.2: the reaction time is 5 hours, and a micro-nano zinc solution is prepared;
and step 3: adding 55 parts by mass of cyclopentadiene epoxy resin and 14 parts by mass of sorbitol into a reaction kettle, heating to 80 ℃, and uniformly stirring to obtain a polymer A;
and 4, step 4: adding 11.5 parts by mass of hydroxymethyl acrylate into the polymer A obtained in the step 3, and stirring and reacting at the rotating speed of 1050 revolutions per minute for 3 hours to obtain a polymer B;
and 5: adding 5 parts by mass of micro-nano zinc solution into 14.5 parts by mass of ethanol, and stirring and dispersing to obtain a dispersion liquid A;
step 6: and (4) adding the dispersion liquid A into the polymer B prepared in the step (4), and fully stirring uniformly to prepare the normal-temperature curing micro-nano zinc long-acting antibacterial mildew preventive.
Example 6
A preparation method of a normal-temperature curing type micro-nano zinc long-acting antibacterial mildew preventive comprises the following steps:
step 1.1: dissolving 50mL of nonylphenol polyoxyethylene ether and 30mL of n-octanol in 120mL of cyclohexane, and stirring with 20mL of isoamyl alcohol and 200mL of deionized water to prepare a WPO (waterborne polyurethane emulsion) reverse microemulsion system;
step 1.2: adding 1000mL of mixed solution of zinc citrate and zinc nitrate with the concentration of 450g/L and 1000mL of hydrazine hydrate solution into 3600mL of WPO reverse microemulsion for mixing, and reacting for 6.5h at 65 ℃ and the rotating speed of 4600rpm to prepare zinc particle solution with the particle size of 10-600 nm;
step 2.1: transferring the prepared zinc particle solution into the next reaction kettle, stirring at 60 ℃, 4600rpm, and introducing high-speed air flow to form a cavitation phenomenon;
step 2.2: the reaction time is 5 hours, and a micro-nano zinc solution is prepared;
and step 3: adding 40 parts by mass of butene epoxy resin and 17.5 parts by mass of glycerol into a reaction kettle, heating to 85 ℃, and uniformly stirring to obtain a polymer A;
and 4, step 4: adding 12.5 parts by mass of hydroxymethyl methacrylate into the polymer A obtained in the step 3, and stirring and reacting for 4 hours at the rotating speed of 1000 rpm to obtain a polymer B;
and 5: adding 4 parts by mass of micro-nano zinc solution into 26 parts by mass of ethanol, and stirring and dispersing to obtain a dispersion liquid A;
step 6: and (4) adding the dispersion liquid A into the polymer B prepared in the step (4), and fully stirring uniformly to prepare the normal-temperature curing micro-nano zinc long-acting antibacterial mildew preventive.
Example 7
According to GB/T21866-.
TABLE 4 antibacterial effect of micro-nano zinc long-acting antibacterial mildew preventive
According to GB/T1741-2007 'determination method for mold resistance of paint film', the mold-proof grade of the normal-temperature curing type micro-nano zinc long-acting antibacterial mildew inhibitor prepared in the embodiments 3-6 of the invention is tested, and the test result is shown in Table 5.
TABLE 5 mould-proof grade of micro-nano zinc long-acting antibacterial mould inhibitor
According to WS/T650-2019 "evaluation method of antibacterial and bacteriostatic effects", the micro-nano zinc long-acting antibacterial mildew inhibitor capable of spraying a film, prepared in examples 3-6, is smeared on an aluminum plate used daily, dried to form a film, wiped with normal clear water, sampled after 7 days, 15 days and 30 days respectively, meanwhile, an untreated aluminum plate is sampled, cultured at 36 +/-1 ℃ for 48 hours, the number of microbial colonies is observed, and the bacteriostatic rate is calculated, wherein the specific results are shown in Table 6, and the forms of the cultured colonies of the micro-nano zinc long-acting antibacterial mildew inhibitor capable of spraying a film, prepared in examples 3-6, after 7 days, 15 days and 30 days are smeared are shown in FIG. 7.
TABLE 6 Long-acting antibacterial effect of the long-acting antibacterial mildew inhibitor containing micro-nano zinc
As can be seen from Table 6, the normal-temperature curing micro-nano zinc long-acting antibacterial mildew preventive has a good long-acting antibacterial effect, and still has 99% of continuous antibacterial effect after daily use for 30 days.
The sterilization and mildew-proof mechanism of the normal-temperature curing micro-nano zinc long-acting antibacterial mildew inhibitor prepared by the invention is as follows:
the antibacterial agent generally needs to be in effective contact with bacteria and the like in a liquid state to have an antibacterial effect, but continuous antibacterial action cannot be performed, the antibacterial liquid is solidified into a film, and zinc particles contained on the surface of the film are in contact with the bacteria and the like to realize antibacterial action without loss, so that the aim of continuous antibacterial action is fulfilled.
According to the invention, a micro-nano zinc solution is used as an antibacterial component, an antibacterial mildew inhibitor is prepared by a dispersant A, a polymer B and the like, and after the antibacterial mildew inhibitor is sprayed, used and solidified into a film, zinc particles on the surface of the film can be induced to generate hydroxyl radicals and active oxygen ions (ROS) with a reducing effect, so that the multiplication capacity of bacterial cells can be damaged, and bacteria can be inhibited or killed; after film formation, zinc particles are attached to the surface of the film, and can perform continuous antibacterial action, so that the antibacterial durability is greatly improved; meanwhile, the zinc plays a role of a drier, so that the antibacterial mildew preventive is solidified into a film at room temperature in the spraying use process, the washing resistance of the antibacterial mildew preventive is improved, the loss of antibacterial components is prevented, and the long-acting antibacterial performance is kept.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of a normal-temperature curing type micro-nano zinc long-acting antibacterial mildew preventive is characterized by comprising the following steps:
step 1: preparing a zinc particle solution by using a micro-emulsion method, wherein the particle size of zinc particles is 10-600 nm;
step 2: transferring the prepared zinc particle solution to the next reaction kettle, and preparing a micro-nano zinc solution by utilizing a cavitation phenomenon;
and step 3: mixing 25-55 parts by mass of an initiator and 10-25 parts by mass of a modifier, and reacting to obtain a polymer A;
and 4, step 4: adding 10-15 parts by mass of acrylic ester into the polymer A obtained in the step (3), stirring and mixing, and reacting to obtain a polymer B;
and 5: adding 2-6 parts by mass of the micro-nano zinc solution prepared in the step 2 into 8.5-41.5 parts by mass of the dispersing agent A, and stirring and dispersing to obtain a dispersion liquid A;
step 6: and (4) adding the dispersion liquid A into the polymer B prepared in the step (4), and fully stirring uniformly to prepare the normal-temperature curing micro-nano zinc long-acting antibacterial mildew preventive.
2. The preparation method of the normal-temperature curing micro-nano zinc long-acting antibacterial mildew inhibitor according to claim 1, wherein the step 1 further comprises the steps of 1.1: dissolving a surfactant in an organic solvent, mixing with a cosurfactant and deionized water, and stirring to prepare a WPO (waterborne polyurethane emulsion) reverse microemulsion system; step 1.2: respectively adding a zinc salt aqueous solution with the concentration of 400-600 g/L and a hydrazine hydrate solution into the WPO reverse-phase microemulsion system, stirring and mixing, reacting at the temperature of 40-80 ℃ and the stirring speed of 2000-5000 rpm for 5-8 h to obtain a zinc particle solution with the particle size of 10-600 nm.
3. The preparation method of the normal-temperature curing micro-nano zinc long-acting antibacterial mildew inhibitor according to claim 2, wherein in the step 1.1, the volume ratio of the total volume of the surfactant, the cosurfactant and the organic solvent to deionized water is 1-4: 1, and the volume ratio of the surfactant, the cosurfactant and the organic solvent is 1-5: 1: 2-4; the volume ratio of the zinc salt aqueous solution to the hydrazine hydrate solution in the step 1.2 is 1:1, and the volume ratio of the hydrazine hydrate solution to the WPO reverse microemulsion system is 1: 3.5-4.
4. The preparation method of the normal-temperature curing micro-nano zinc long-acting antibacterial mildew inhibitor according to claim 2, wherein in the step 1.1, the surfactant is a nonionic surfactant, and the organic solvent is one or more of alkane and cycloalkane; the cosurfactant is fatty alcohol; the zinc salt in the step 1.2 is one or more of zinc sulfate, zinc nitrate, zinc citrate and zinc gluconate.
5. The preparation method of the normal-temperature curing micro-nano zinc long-acting antibacterial mildew preventive according to claim 4, wherein the non-ionic surfactant is one or more of polyoxyethylene nonyl phenyl ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether and high-carbon fatty polyoxyethylene ether; the organic solvent is cyclohexane; the cosurfactant is one or more of isoamyl alcohol, n-heptanol, n-octanol, n-nonanol, n-decanol and cetyl alcohol.
6. The preparation method of the normal-temperature curing micro-nano zinc long-acting antibacterial mildew inhibitor according to claim 1, wherein the step 2 further comprises:
step 2.1: transferring the zinc particle solution prepared in the step 1 to a next reaction kettle, stirring at 60 ℃, wherein the stirring speed is 2000-5000 rpm, and introducing high-speed air flow to form a cavitation phenomenon;
step 2.2: reacting for 5 hours to prepare the micro-nano zinc solution.
7. The preparation method of the normal-temperature curing micro-nano zinc long-acting antibacterial mildew inhibitor according to claim 1, wherein the reaction temperature in the step 3 is 70-95 ℃.
8. The preparation method of the normal-temperature curing micro-nano zinc long-acting antibacterial mildew preventive according to claim 1, wherein the initiator in the step 3 is one or more of diphenol propane epoxy resin, butylene epoxy resin and cyclopentadiene epoxy resin; the modifier in the step 3 is one or more of pentaerythritol, glycerol, xylitol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, diethyl toluene diamine and sorbitol.
9. The preparation method of the normal-temperature curing micro-nano zinc long-acting antibacterial mildew inhibitor according to claim 1, wherein the stirring speed in the step 4 is 900-1200 rpm, and the reaction time is 2-6 hours; the acrylate in the step 4 is one or more of methyl acrylate, ethyl acrylate, 2-methyl methacrylate, 2-ethyl methacrylate, hydroxyethyl acrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate and hydroxymethyl methacrylate.
10. The preparation method of the normal-temperature curing micro-nano zinc long-acting antibacterial mildew inhibitor according to claim 1, wherein the dispersing agent A in the step 5 is one or more of ethylene glycol, ethanol, butanol and water.
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