CN113652166A - Preparation method of antibacterial and antiviral environment-friendly interior wall finishing coating and product thereof - Google Patents
Preparation method of antibacterial and antiviral environment-friendly interior wall finishing coating and product thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention relates to a preparation method of an antibacterial and antiviral environment-friendly interior wall modification coating and a product thereof, and the preparation method comprises the preparation of nano inorganic antibacterial and antiviral powder, the preparation of pure water polyurethane acrylate nano narrow-band emulsion and the preparation of pure water nano antibacterial and antiviral coating. The pure water antibacterial and antiviral interior wall decorating paint is prepared by taking pure water nano-grade dendritic copolymer as a base material, has high fullness of coating, good film covering effect, excellent water resistance, air permeability, water impermeability and excellent mildew-proof effect, ensures that the wall decorating surface is not easy to fall dust, stains are not easy to attach and is easy to clean, has lasting antibacterial and antiviral capacity, has the antibacterial rate of 99 percent for large intestine, golden yellow and the like, and has the H1N1 virus killing rate of 92.3 percent.
Description
Technical Field
The invention belongs to the technical field of coatings, relates to an antibacterial and antiviral functional coating, and particularly relates to a preparation method of an antibacterial and antiviral interior wall coating and a product thereof.
Background
The most common interior wall decorative coating at present is latex paint, which is a large class of synthetic resin emulsion coating represented by acrylate copolymer emulsion, can continuously release volatile organic compounds such as formaldehyde, and the concentration of harmful gas can be several times or even dozens of times higher than that of the exterior. Meanwhile, in hospitals, schools, kindergartens, catering units and other public places with dense people flow, the spread speed of germs (including new coronavirus and the like) is high, cross infection and infectious disease spread are easily caused, and indoor air pollution is also aggravated. In addition, the public places use a lot of electrical equipment, and fire safety is very important; during a fire, the conventionally used interior finishing materials burn and release a large amount of toxic gas, resulting in death of people after suffocation. The 'building interior decoration design fire protection code' GB50222-2017, which is implemented from 4 months and 1 days in 2018, also stipulates that interior decoration materials of industrial and civil buildings need to reach the A-level fire protection standard. Organic coatings such as latex paint and the like cannot meet the requirement of fire-proof grade, and the organic coatings can be combusted, decomposed and release toxic gases at high temperature to harm the life of people; at present, the interior wall decorative coating which is high in quality, safe, healthy, antibacterial, antiviral, environment-friendly, fireproof, easy to clean and the like and can adapt to green ecological construction of public places such as hospitals, schools, kindergartens, catering units and the like is lacked in the market.
The Chinese invention patents with the publication numbers of 202010845698.2 and 202010803801.7 disclose technical schemes of antiviral interior wall coatings through the search of existing patent documents, but the patents all use organic resins such as water-based acrylic resin and/or styrene-acrylic resin/EVA/vinyl acetate-acrylic emulsion as film forming substances, film forming additives are required to be added in the production and film forming processes, harmful organic solvents exist and remain, and the health of users is continuously influenced. And the existing interior wall decorative coating of organic resin has low hardness after film forming, poor washing resistance and short service life, and the wall surface is not easy to clean after being soiled.
The Chinese patent with application number 202010640905.0 discloses a technical scheme of an antiviral interior wall coating, which takes composite silicate as a film forming substance, and the washing resistance of the coating can only reach about 6000 times generally; the waterproof performance is poor, and the mildew is easy to occur in a humid environment; and the coating is not acid-resistant and cracks and falls off when meeting acid.
The Chinese patent with application number 202010615798.6 discloses a long-acting slow-release bactericidal antiviral coating, a preparation method and an application technical scheme thereof, wherein inorganic materials such as calcium carbonate and nano-silica are adopted as film forming substances, and although the scheme can be used for long-acting slow-release bactericidal antiviral agents, the wall surface has poor water resistance, and is not easy to clean after being soiled, so that the appearance is influenced.
The commonly used antibacterial materials at present comprise inorganic antibacterial materials and organic antibacterial materials, the inorganic antibacterial materials are commonly used metal ion type antibacterial agents taking silver ions and the like as active components and photocatalytic type antibacterial agents taking titanium dioxide as a representative component, but the antibacterial effect of the silver ions is greatly influenced by light and heat, the titanium dioxide can play the antibacterial effect under the irradiation of near ultraviolet light, and the titanium dioxide is difficult to settle and recover and is limited in application. Quaternary ammonium salt, halogen amine and chitosan antibacterial agents are commonly used as organic antibacterial materials, but the quaternary ammonium salt antibacterial agent is a low-molecular antibacterial agent with poor heat resistance and high toxicity; the halamine antibacterial agent is a high-molecular antibacterial agent, has poor compatibility and limited application range; the chitosan antibacterial agent is a natural antibacterial agent, has poor water solubility and is difficult to be used as an additive. In view of the disadvantages of the conventional antibacterial materials, a new antibacterial and antiviral material with stability, safety and broad spectrum is needed.
The two-dimensional nanosheet layers are combined through Van der Waals force, and metal ions such as silver, zinc, copper and the like are absorbed in the two-dimensional nanosheet layers, so that the stability of the antibacterial agent can be improved. However, the interlayer spacing is often too small, and silver, zinc and copper ions are generally difficult to enter the two-dimensional nanosheet layers due to various reasons such as the surface tension of the solution, and the loading rate is affected.
To solve the above problems, we need a new antibacterial material or a new structural design, which ensures that the antibacterial material can slowly and stably release the active ingredients, has higher stability, and can greatly delay the excessive migration of the active ingredients. Therefore, the development of the antibacterial and antiviral interior wall finishing coating with low cost and zero VOC has very important significance.
Disclosure of Invention
Aiming at the defects of insufficient antiviral performance, poor stability, easy cracking of inner wall modification paint, environmental pollution and the like of the existing antibacterial and antiviral material, the invention aims to provide a preparation method of the antibacterial and antiviral inner wall coating, and a preparation method of the layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral inner wall modification paint.
Yet another object of the present invention is to: provides the antibacterial and antiviral interior wall coating product prepared by the method.
The purpose of the invention is realized by the following scheme: a preparation method of an antibacterial and antiviral environment-friendly interior wall finishing coating comprises the following steps:
(1) preparation of nano inorganic antibacterial antiviral powder
According to the mass ratio of 1: (0.01-100): (0.01-100): (0.01-100): (0.01-100): (1-1000) weighing inorganic silver salt, zinc salt or copper salt, a modifier, a complexing agent and a solvent, firstly adding the silver salt, the zinc salt, the copper salt, the modifier and the complexing agent into the solvent, and modifying and complexing metal ions by adopting an ultrasonic-assisted high-speed shearing stirring mode to prepare a metastable complex silver-zinc-copper composite ionic solution, so that the metastable complex silver-zinc-copper composite ionic solution can more easily enter between two-dimensional nanosheet layers;
adding a two-dimensional nano layered material into the prepared metastable state complex silver-zinc-copper composite ion solution to enable the mass ratio of silver salt to the two-dimensional nano layered material to be 1 (1-10000), stirring and dispersing, and adsorbing the metastable state complex silver-zinc-copper composite ion to the interlayer of the two-dimensional nano layered material through unsaturated adsorption to obtain a mixed solution; transferring the mixed solution into a stainless steel reaction kettle, carrying out hydrothermal reaction treatment for 4-72 hours at the temperature of 373-473K in a high-pressure reaction kettle, or carrying out stirring reflux reaction for 12-72 hours at the temperature of 373-403K in a normal-pressure reaction kettle, filtering or centrifuging after the reaction is finished to obtain a precipitate, and centrifuging and drying to obtain the layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material;
(2) preparing pure water polyurethane acrylate nano narrow-band emulsion:
dehydrating 2-7 parts of oligomer polyol at 70-100 ℃ for 80-160 min in vacuum, dropwise adding 2-9 parts of diisocyanate, and reacting for 60-90 min under heat preservation; adding 1-5 parts of hydrophilic chain extender at 30-80 ℃, and reacting for 60-90 min in a heat preservation manner; then 3-10 parts of acrylic monomers are dropped, the reaction is carried out for 15-30 min at the temperature of 40-80 ℃, then the temperature is reduced to 30-75 ℃, 1-5 parts of neutralizing agent are added for reaction for 20-40 min, 0.5-3 parts of catalyst and 1-5 parts of initiator are added at constant temperature, and the reaction is carried out for 30-50 min; adding 5-10 parts of deionized water, stirring at the rotating speed of 1000-3000 rpm for 20-40 min, and emulsifying to obtain pure water polyurethane acrylate nano narrow-band emulsion;
(3) preparation of water-based nano antibacterial and antiviral paint
Adjusting the rotating speed of a dispersion machine to 200-600 rpm, weighing 5-10 parts by weight of pure water polyurethane acrylate nano narrow-band emulsion according to the material ratio, and sequentially adding 5-15 parts by weight of functional additive and 1-3 parts by weight of thickener; 2-4 parts by weight of inorganic antibacterial and antiviral powder, stirring and dispersing for 10-30 min to meet the fineness requirement, adjusting the rotation speed to 1200-2000 rpm, and stirring for 60 min at 25-40 ℃; reducing the rotating speed, stirring and dispersing at 300-800 rpm for 10-30 min, and finally adding 0.2-1 part by weight of defoaming agent to prepare the pure water antibacterial antiviral interior wall modification coating.
On the basis of the scheme, in the step (1), the silver salt is any one or a mixture of more of silver nitrate, silver fluoride, silver chlorate, silver perchlorate and silver bicarbonate; the zinc salt is any one or a mixture of zinc chloride, zinc bromide, zinc nitrate, zinc carbonate, zinc acetate and zinc sulfate; the copper salt is any one or a mixture of more of copper chloride, copper sulfate and copper nitrate.
Preferably, in the step (1), the modifier is any one or a mixture of several of ethylenediamine, 2-bipyridine, 1, 10-diazophenanthrene, nitrilotriacetic acid, ethylenediamine tetraacetic acid, dithizone, 8-hydroxyquinoline, phenanthroline, potassium sodium tartrate, ammonium citrate and polyphosphate.
Preferably, in the step (1), the complexing agent is any one or a mixture of more of ethylenediamine tetraacetic acid, citric acid, dibenzo-18-crown-6, diethylenetriamine pentaacetic acid, benzo-15-crown-5, inositol phosphate, ethylene glycol-bis- (2-aminoethyl) tetraacetic acid, nitrilotriacetic acid, diethylenetriamine pentaacetic acid, beta-mercaptoethylamine hydrochloride, sodium hydroxyethylidene diphosphonate, PN sodium hydroxymethyl sulfonate and diethylenetriamine pentaethanol.
Preferably, in the step (1), the solvent is any one or a mixture of several of deionized water, ethanol, isopropanol, acetone, ethylene glycol and dimethylformamide.
Preferably, in the step (1), the ultrasonic power is 1000-8000W; the high-speed shearing dispersion adopts a Fluke FA25 high-shear dispersion emulsifying machine, the rotating speed is 5000-30000 r/min, and the processing time is 0.5-10 hours.
On the basis of the scheme, in the step (1), the two-dimensional nano layered material is any one or a mixture of more of nickel cobalt lithium manganate, boron nitride, molybdenum sulfide, zirconium hydrogen phosphate, mica, vermiculite, graphite, black phosphorus and graphite-like phase carbon nitride. .
On the basis of the scheme, in the step (2), the pure water polyurethane acrylate narrowband nano emulsion is prepared from the following raw materials in parts by weight:
2-7 parts of oligomer polyol;
2-9 parts of diisocyanate;
1-5 parts of a hydrophilic chain extender;
3-10 parts of acrylic monomers;
1-5 parts of a neutralizing agent;
0.5-3 parts of a catalyst;
1-5 parts of an initiator;
5 to 10 parts of deionized water,
the preparation method comprises the following steps: dehydrating 2-7 parts of oligomer polyol at 70-100 ℃ for 80-160 min in vacuum, dropwise adding 2-9 parts of diisocyanate, and reacting for 60-90 min under heat preservation; adding 1-5 parts of hydrophilic chain extender at 40-80 ℃, and reacting for 60-90 min in a heat preservation manner; then 3-10 parts of acrylic monomers are dropped, the reaction is carried out for 15-30 min at the temperature of 40-80 ℃, then the temperature is reduced to 30-75 ℃, 1-5 parts of neutralizing agent are added for reaction for 20-40 min, 0.5-3 parts of catalyst and 1-5 parts of initiator are added at constant temperature, and the reaction is carried out for 30-50 min; adding 5-10 parts of deionized water, stirring at the rotating speed of 1000-3000 rpm for 20-40 min, and emulsifying to obtain the pure water polyurethane acrylate nano narrow-band emulsion.
Preferably, the oligomer polyol is selected from one or more of polyoxypropylene glycol, polyvinyl alcohol, polyhexamethylene adipate, polytetrahydrofuran diol or castor oil; the diisocyanate is one or more than two of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate or diphenylmethane diisocyanate; the hydrophilic chain extender is selected from one or two of 2, 2-dimethylolpropionic acid or 2, 2-dimethylolbutyric acid; the acrylic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate or hydroxypropyl acrylate; the neutralizer is one or more than two selected from triethylamine, ammonia water, sodium hydroxide, hydrochloric acid or epoxy chloropropane; the catalyst is selected from one or more of isooctyl acrylate, dibutyltin dilaurate or 6-hexanediol diacrylate; the initiator is one or more than two of benzoin ethyl ether, 2,4, 6-trimethyl benzoyl-diphenyl phosphorus oxide, azodiisobutyronitrile or 1-hydroxycyclohexyl phenyl ketone.
On the basis of the scheme, in the step (3), the preparation method of the antibacterial and antiviral interior wall modification coating comprises the following steps: adjusting the rotating speed of a dispersion machine to 200-600 rpm, weighing 5-10 parts by weight of pure water polyurethane acrylate nano narrow-band emulsion according to the material ratio, sequentially adding 5-15 parts by weight of functional additive, 1-3 parts by weight of thickening agent and 2-4 parts by weight of inorganic antibacterial and antiviral powder, stirring and dispersing for 10-30 min to meet the fineness requirement, adjusting the rotating speed to 1200-2000 rpm, and stirring for 60 min at 25-40 ℃; reducing the rotating speed, stirring and dispersing at 300-800 rpm for 10-30 min, and finally adding 0.2-1 part by weight of defoaming agent to obtain the pure water nano reflective insulation coating.
Preferably, the thickener is one or more selected from methylcellulose, hydroxypropyl methylcellulose, polyvinyl alcohol, polyethylene oxide, carbomer resin, sodium polyacrylate or polyacrylate copolymer emulsion. The defoaming agent is selected from one or more of emulsified silicone oil, fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene ether; the functional assistant is sericite.
Compared with the prior art, the pure water polyurethane acrylate narrowband nano emulsion has the advantages of zero VOC emission, no pollution, easier film formation and low cost. The layered material unsaturated silver-zinc-copper ion loaded composite antibacterial and antiviral material prepared by the method can quickly adsorb bacteria and viruses to enter the interlayer when in use, and then utilize the silver-zinc-copper ions to kill the bacteria and the viruses; on the other hand, the problem that the common silver ion antibacterial material is easy to oxidize and discolor to generate black spots can be solved, and compared with the common silver ion antibacterial material, the silver ion antibacterial material has less dissolved substances and longer service life. Even, the broad spectrum of the antibacterial and antiviral materials can be further enhanced by processing the materials in a compounding way with a weak light photocatalysis material and firing the materials at high temperature to form the layered composite antibacterial and antiviral material.
Drawings
FIG. 1: high power transmission electron micrograph of the antibacterial and antiviral powder prepared from example 2.
Detailed Description
The invention is further illustrated by the following examples, which are intended only for a better understanding of the contents of the invention. The examples given therefore do not limit the scope of the invention.
Example 1
An antibacterial and antiviral environment-friendly interior wall finishing coating is prepared by the following steps:
(1) preparation of nano inorganic antibacterial antiviral powder
According to the mass ratio of 1: 0.01: 0.01: 0.01: 0.01: 1, weighing silver nitrate, zinc chloride or copper sulfate, modifier nitrilotriacetic acid, complexing agent benzo-15-crown ether-5 and deionized water, firstly adding silver salt, zinc salt, copper salt, modifier and complexing agent into the deionized water, and modifying and complexing metal ions by adopting ultrasonic assistance with the power of 1000W and high-speed shearing and stirring treatment time of 5000 r/min for 0.5h to prepare modified metastable complex silver-zinc-copper composite ionic solution, so that the modified metastable complex silver-zinc-copper composite ionic solution can more easily enter between two-dimensional nanosheet layers;
adding a two-dimensional nano layered material zirconium hydrogen phosphate into the prepared metastable state complex silver-zinc-copper composite ion solution to enable the mass ratio of silver salt to the two-dimensional nano layered material to be 1:1, adsorbing metastable state complex silver-zinc-copper composite ions to the layers of the two-dimensional nano layered material through unsaturated adsorption after stirring and dispersing, transferring the mixed solution into a stainless steel reaction kettle, carrying out hydrothermal reaction treatment for 4 hours at the temperature of 373K in a high-pressure reaction kettle, or carrying out stirring reflux reaction for 12 hours at the temperature of 373K in a normal-pressure reaction kettle, obtaining a precipitate product by adopting a filtering or centrifuging method after the reaction is finished, and obtaining the layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material after centrifugation and drying;
(2) preparing pure water polyurethane acrylate nano narrow-band emulsion:
4 parts of oligomer polyol polyoxypropylene glycol is subjected to vacuum dehydration for 150 min at the temperature of 80 ℃,4 parts of isophorone diisocyanate is dripped, and the heat preservation reaction is carried out for 90 min; adding 5 parts of hydrophilic chain extender 2, 2-dimethylolpropionic acid at 40 ℃, and reacting for 90 min under the condition of heat preservation; then 6 parts of acrylic monomer methacrylic acid is dripped in, the reaction is carried out for 30min under the temperature of 40 ℃, then the temperature is reduced to 45 ℃,2 parts of neutralizer NaOH are added for reaction for 30min, 0.8 part of catalyst isooctyl acrylate and 1 part of initiator azobisisobutyronitrile are added at constant temperature, and the reaction is carried out for 30 min; adding 10 parts of deionized water, stirring at the rotating speed of 3000 rpm for 30min, and emulsifying to obtain pure water polyurethane acrylate nano narrow-band emulsion;
(3) preparation of water-based nano antibacterial and antiviral paint
Adjusting the rotating speed of a dispersion machine to 300rpm, weighing 5 parts by weight of pure water polyurethane acrylate nano narrow-band emulsion according to the material ratio, and sequentially adding 10 parts by weight of functional assistant sericite and 2.2 parts by weight of thickener methyl cellulose; and 2 parts by weight of the inorganic antibacterial and antiviral powder prepared in the step (1), stirring and dispersing for 20 min to meet the fineness requirement, adjusting the rotating speed to 2000 rpm, and stirring for 60 min at 30 ℃; reducing the rotating speed, stirring and dispersing for 30min at 300rpm, and finally adding 0.2 part by weight of defoaming agent emulsified silicone oil to prepare the pure water antibacterial antiviral interior wall finishing coating.
The antibacterial rate test result of the coating prepared in the embodiment is as follows: 99.99% of colibacillus, 99.91% of staphylococcus aureus, 99.99% of klebsiella pneumoniae and 91.30% of candida albicans. The antiviral effect is as follows: H1N1 was 89.8%.
Example 2
An antibacterial and antiviral environment-friendly interior wall finishing coating is similar to the step of the example 1, and is prepared by the following steps:
(1) preparation of nano inorganic antibacterial antiviral powder
According to the mass ratio of 1: 20: 30: 50: 50: 500 weighing inorganic silver chlorate serving as a silver salt, zinc carbonate serving as a zinc salt, copper chloride serving as a copper salt, sodium potassium tartrate serving as a modifier, diethylenetriamine pentaacetic acid serving as a complexing agent and ethanol serving as a solvent, adding the silver salt, the zinc salt, the copper salt, the modifier and the complexing agent into the solvent, and modifying and complexing metal ions by adopting a mode of ultrasonic-assisted high-speed shearing and stirring at the power of 3000W at 15000 r/min for 3h to prepare a modified metastable-state silver-zinc-copper complex ion solution so that the modified metastable-state silver-zinc-copper complex ion solution can more easily enter between two-dimensional nanosheet layers;
adding two-dimensional nano layered material graphite phase carbon nitride into the prepared metastable state complex silver-zinc-copper composite ion solution to enable the mass ratio of silver salt to the two-dimensional nano layered material to be 1:80, stirring and dispersing, adsorbing metastable state complex silver-zinc-copper composite ions to the layers of the two-dimensional nano layered material through unsaturated adsorption, transferring the mixed solution into a stainless steel reaction kettle, carrying out hydrothermal reaction treatment for 72 hours at the temperature of 473K in the high-pressure reaction kettle, obtaining a precipitate product by adopting a filtering or centrifuging method after the reaction is finished, and centrifuging and drying to obtain the layered material unsaturated silver-zinc-copper ion loaded composite antibacterial and antiviral powder material; the high power transmission electron microscope photo of the prepared antibacterial and antiviral powder is shown in figure 1;
(2) preparing pure water polyurethane acrylate nano narrow-band emulsion:
dehydrating 4 parts of oligomer polyalcohol polyvinyl alcohol at 80 ℃ for 150 min in vacuum, dropwise adding 4 parts of toluene diisocyanate, and reacting for 90 min under heat preservation; adding 5 parts of hydrophilic chain extender 2, 2-dimethylolbutyric acid at 30 ℃, and reacting for 90 min under the condition of heat preservation; then 6 parts of acrylic monomer hydroxyethyl acrylate is dropped in, the reaction is carried out for 30min at the temperature of 40 ℃, then the temperature is reduced to 45 ℃,2 parts of neutralizer NaOH are added for reaction for 30min, 0.8 part of catalyst isooctyl acrylate and 1 part of initiator azobisisobutyronitrile are added at constant temperature, and the reaction is carried out for 30 min; adding 10 parts of deionized water, stirring at the rotating speed of 3000 rpm for 30min, and emulsifying to obtain pure water polyurethane acrylate nano narrow-band emulsion;
(3) preparation of water-based nano antibacterial and antiviral paint
Adjusting the rotating speed of a dispersion machine to 300rpm, weighing 5 parts by weight of pure water polyurethane acrylate narrowband nano emulsion according to the material ratio, sequentially adding 10 parts by weight of sericite as a functional auxiliary agent, 2.2 parts by weight of methylcellulose and 0.2 part by weight of polyvinyl alcohol as a thickening agent, and 4 parts by weight of inorganic antibacterial and antiviral powder prepared in the step (1), stirring and dispersing for 20 min until the fineness requirement is met, adjusting the rotating speed to 2000 rpm, and stirring for 60 min at 30 ℃; reducing the rotating speed, stirring and dispersing for 30min at 300rpm, and finally adding 0.2 part by weight of defoaming agent emulsified silicone oil to prepare the pure water antibacterial antiviral interior wall finishing coating.
The antibacterial rate test result of the coating prepared in the embodiment is as follows: 99.99% of colibacillus, 99.91% of staphylococcus aureus, 99.19% of klebsiella pneumoniae and 98.30% of candida albicans. The antiviral effect is as follows: H1N1 was 90.7%.
Example 3
An antibacterial and antiviral environment-friendly interior wall finishing coating is similar to the step of the example 1, and is prepared by the following steps:
(1) preparation of nano inorganic antibacterial antiviral powder
According to the mass ratio of 1: 5: 2: 100: 100: 300 weighing inorganic silver salt silver bicarbonate, zinc salt zinc acetate, copper salt copper nitrate, modifier dithizone, complexing agent PN (pseudo-noise) sodium hydroxymethyl sulfonate and solvent isopropanol, firstly adding silver salt, zinc salt, copper salt, modifier and complexing agent into the solvent, and modifying and complexing metal ions by adopting a mode of ultrasonic assistance of 30000 r/min with the power of 8000W and high-speed shearing stirring treatment time of 10h to prepare a modified metastable-state complex silver-zinc-copper composite ionic solution, so that the modified metastable-state complex silver-zinc-copper composite ionic solution can more easily enter between two-dimensional nanosheet layers;
adding a two-dimensional nano layered material nickel cobalt lithium manganate into the prepared metastable state complex silver zinc copper composite ion solution to enable the mass ratio of the silver salt to the two-dimensional nano layered material to be 1:10000, stirring and dispersing, and adsorbing the metastable state complex silver zinc copper composite ion to the interlayer of the two-dimensional nano layered material through unsaturated adsorption to obtain a mixed solution; transferring the mixed solution into a stainless steel reaction kettle, stirring and refluxing the mixed solution in a normal pressure reaction kettle at the temperature of 403K for reaction for 18 hours, obtaining a precipitate product by adopting a filtering or centrifuging method after the reaction is finished, and centrifuging and drying the precipitate product to obtain the layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material;
(2) preparing pure water polyurethane acrylate nano narrow-band emulsion:
dehydrating 4 parts of oligomer polyalcohol polytetrahydrofuran diol at 80 ℃ for 150 min in vacuum, dropwise adding 4 parts of diphenylmethane diisocyanate, and reacting for 90 min under heat preservation; adding 5 parts of hydrophilic chain extender 2, 2-dimethylolbutyric acid at 30 ℃, and reacting for 90 min under the condition of heat preservation; then 6 parts of acrylic monomer hydroxyethyl acrylate is dropped in, the reaction is carried out for 30min at the temperature of 40 ℃, then the temperature is reduced to 45 ℃,2 parts of neutralizer NaOH are added for reaction for 30min, 0.8 part of catalyst isooctyl acrylate and 1 part of initiator azobisisobutyronitrile are added at constant temperature, and the reaction is carried out for 30 min; adding 10 parts of deionized water, stirring at the rotating speed of 3000 rpm for 30min, and emulsifying to obtain pure water polyurethane acrylate nano narrow-band emulsion;
(3) preparation of water-based nano antibacterial and antiviral paint
Adjusting the rotating speed of a dispersion machine to 300rpm, weighing 5 parts by weight of pure water polyurethane acrylate nano narrow-band emulsion according to the material ratio, sequentially adding 10 parts by weight of functional assistant sericite, 2.2 parts by weight of thickening agent methylcellulose and 0.2 part by weight of fatty alcohol-polyoxyethylene ether, and 3 parts by weight of the inorganic antibacterial and antiviral powder prepared in the step (1), stirring and dispersing for 20 min to meet the fineness requirement, adjusting the rotating speed to 2000 rpm, and stirring for 60 min at 30 ℃; reducing the rotating speed, stirring and dispersing for 30min at 300rpm, and finally adding 0.2 part by weight of defoaming agent emulsified silicone oil to prepare the pure water antibacterial antiviral interior wall finishing coating.
The antibacterial rate test result of the coating prepared in the embodiment is as follows: 99.99% of colibacillus, 99.99% of staphylococcus aureus, 99.99% of klebsiella pneumoniae and 99.30% of candida albicans. The antiviral effect is as follows: H1N1 was 92.3%.
Claims (10)
1. A preparation method of an antibacterial and antiviral environment-friendly interior wall finishing coating is characterized by comprising the following specific steps:
(1) preparation of nano inorganic antibacterial antiviral powder
According to the mass ratio of 1: (0.01-100): (0.01-100): (0.01-100): (0.01-100): (1-1000) weighing inorganic silver salt, zinc salt or copper salt, a modifier, a complexing agent and a solvent, firstly adding the silver salt, the zinc salt, the copper salt, the modifier and the complexing agent into the solvent, and modifying and complexing metal ions by adopting an ultrasonic-assisted high-speed shearing stirring mode to prepare a metastable complex silver-zinc-copper composite ionic solution, so that the metastable complex silver-zinc-copper composite ionic solution can more easily enter between two-dimensional nanosheet layers;
adding a two-dimensional nano layered material into the prepared metastable state complex silver-zinc-copper composite ion solution to enable the mass ratio of silver salt to the two-dimensional nano layered material to be 1 (1-10000), adsorbing metastable state complex silver-zinc-copper composite ions to the layers of the two-dimensional nano layered material through unsaturated adsorption after stirring and dispersing, transferring the mixed solution into a stainless steel reaction kettle, carrying out hydrothermal reaction treatment for 4-72 hours at the temperature of 373-473K in the high-pressure reaction kettle, or carrying out stirring reflux reaction for 12-72 hours at the temperature of 373-403K in a normal-pressure reaction kettle, obtaining a precipitation product by adopting a filtering or centrifuging method after the reaction is finished, and obtaining the layered material unsaturated load silver-zinc-copper ion composite antibacterial antiviral material after centrifugation and drying;
(2) preparing pure water polyurethane acrylate nano narrow-band emulsion:
dehydrating 2-7 parts of oligomer polyol at 70-100 ℃ for 80-160 min in vacuum, dropwise adding 2-9 parts of diisocyanate, and reacting for 60-90 min under heat preservation; adding 1-5 parts of hydrophilic chain extender at 30-80 ℃, and reacting for 60-90 min in a heat preservation manner; then 3-10 parts of acrylic monomers are dropped, the reaction is carried out for 15-30 min at the temperature of 40-80 ℃, then the temperature is reduced to 30-75 ℃, 1-5 parts of neutralizing agent are added for reaction for 20-40 min, 0.5-3 parts of catalyst and 1-5 parts of initiator are added at constant temperature, and the reaction is carried out for 30-50 min; adding 5-10 parts of deionized water, stirring at the rotating speed of 1000-3000 rpm for 20-40 min, and emulsifying to obtain pure water polyurethane acrylate nano narrow-band emulsion;
(3) preparation of water-based nano antibacterial and antiviral paint
Adjusting the rotating speed of a dispersion machine to 200-600 rpm, weighing 5-10 parts by weight of pure water polyurethane acrylate nano narrow-band emulsion according to the material ratio, and sequentially adding 5-15 parts by weight of functional additive and 1-3 parts by weight of thickener; 2-4 parts by weight of inorganic antibacterial and antiviral powder, stirring and dispersing for 10-30 min to meet the fineness requirement, adjusting the rotation speed to 1200-2000 rpm, and stirring for 60 min at 25-40 ℃; reducing the rotating speed, stirring and dispersing at 300-800 rpm for 10-30 min, and finally adding 0.2-1 part by weight of defoaming agent to prepare the pure water antibacterial antiviral interior wall modification coating.
2. The preparation method of the antibacterial and antiviral environment-friendly interior wall finishing coating as claimed in claim 1, wherein in the step (1), the silver salt is any one or a mixture of several of silver nitrate, silver fluoride, silver chlorate, silver perchlorate and silver bicarbonate; the zinc salt is any one or a mixture of zinc chloride, zinc bromide, zinc nitrate, zinc carbonate, zinc acetate and zinc sulfate; the copper salt is any one or a mixture of more of copper chloride, copper sulfate and copper nitrate.
3. The preparation method of the antibacterial and antiviral environment-friendly interior wall finishing coating as claimed in claim 1, characterized in that; in the step (1), the modifier is any one or a mixture of more of ethylenediamine, 2-bipyridine, 1, 10-diazophenanthrene, nitrilotriacetic acid, ethylenediamine tetraacetic acid, dithizone, 8-hydroxyquinoline, phenanthroline, potassium sodium tartrate, ammonium citrate and polyphosphate.
4. The method for preparing the antibacterial and antiviral environment-friendly interior wall finishing coating according to claim 1, wherein in the step (1), the complexing agent is any one or a mixture of more of ethylenediamine tetraacetic acid, citric acid, dibenzo-18-crown-6, diethylenetriamine pentaacetic acid, benzo-15-crown-5, inositol phosphate, ethylene glycol-bis- (2-aminoethyl) tetraacetic acid, nitrilotriacetic acid, diethylenetriamine pentaacetic acid, beta-mercaptoethylamine hydrochloride hydroxyethylidene diphosphonic acid sodium, PN (p-methyl) sodium hydroxymethanesulfonate, and diethylenetriamine pentaethanol.
5. The preparation method of the antibacterial and antiviral environment-friendly interior wall finishing coating as claimed in claim 1, characterized in that; in the step (1), the solvent is any one or a mixture of several of deionized water, ethanol, isopropanol, acetone, ethylene glycol and dimethylformamide.
6. The preparation method of the antibacterial and antiviral environment-friendly interior wall finishing coating as claimed in claim 1, wherein in the step (1), the ultrasonic power is 1000-8000W; the high-speed shearing dispersion adopts a Fluke FA25 high-shear dispersion emulsifying machine, the rotating speed is 5000-30000 r/min, and the processing time is 0.5-10 hours.
7. The preparation method of the antibacterial and antiviral environment-friendly interior wall finishing coating as claimed in claim 1, wherein in the step (1), the two-dimensional nano-layered material is any one or a mixture of more of nickel cobalt lithium manganate, boron nitride, molybdenum sulfide, zirconium hydrogen phosphate, mica, vermiculite, graphite, black phosphorus and graphite-like phase carbon nitride.
8. The method for preparing the antibacterial and antiviral environment-friendly interior wall finishing coating according to claim 1, wherein the oligomer polyol in the step (2) is one or more selected from polyoxypropylene glycol, polyvinyl alcohol, polyhexamethylene adipate, polytetrahydrofuran diol and castor oil; the diisocyanate is selected from one or more than two of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate or diphenylmethane diisocyanate; the hydrophilic chain extender is selected from one or two of 2, 2-dimethylolpropionic acid or 2, 2-dimethylolbutyric acid; the acrylic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate or hydroxypropyl acrylate; the neutralizing agent is one or more than two of triethylamine, ammonia water, sodium hydroxide, hydrochloric acid or epoxy chloropropane; the catalyst is selected from one or more of isooctyl acrylate, dibutyltin dilaurate or 6-hexanediol diacrylate; the initiator is one or more than two of benzoin ethyl ether, 2,4, 6-trimethyl benzoyl-diphenyl phosphorus oxide, azodiisobutyronitrile or 1-hydroxycyclohexyl phenyl ketone.
9. The method for preparing the antibacterial and antiviral environment-friendly interior wall finishing coating as claimed in claim 1, wherein the thickener in the step (3) is one or more selected from methylcellulose, hydroxypropyl methylcellulose, polyvinyl alcohol, polyethylene oxide, carbomer resin, sodium polyacrylate or polyacrylate copolymer emulsion; the defoaming agent is selected from one or more of emulsified silicone oil, fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene ether; the functional assistant is sericite.
10. An antibacterial and antiviral environment-friendly interior wall finishing coating, characterized by being prepared according to the method of any one of claims 1 to 9.
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Application publication date: 20211116 |