CN102511503B - Efficient and environmentally-friendly antibacterial and mildewproof inorganic composite nano-powder slurry and its preparation method - Google Patents
Efficient and environmentally-friendly antibacterial and mildewproof inorganic composite nano-powder slurry and its preparation method Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 92
- 239000002002 slurry Substances 0.000 title claims abstract description 83
- 239000011858 nanopowder Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 47
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002270 dispersing agent Substances 0.000 claims abstract description 39
- 239000011787 zinc oxide Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 13
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 13
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000292 calcium oxide Substances 0.000 claims abstract description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 11
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 239000000843 powder Substances 0.000 claims description 73
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- 239000000126 substance Substances 0.000 claims description 27
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Relateing to the field of antibacterial materials, the invention specifically provides an efficient and environmentally-friendly antibacterial and mildewproof inorganic composite nano-powder slurry obtained through compounding nano-magnesium oxide and other nano-inorganic materials and its preparation method. The nano-powder slurry takes nano-magnesium oxide as the main body, which is then compounded with one or more inorganic materials of nano-zinc oxide, nano-titanium oxide, nano-copper oxide, nano-cuprous oxide, nano-silver oxide, nano-zinc sulfide, nano-zirconium oxide, nano-yttrium oxide, nano-alumina, and nano-calcium oxide so as to form the nano-powder slurry, which comprises, by weight percent: 0.1-40% of nano-magnesium oxide, 0.01-40% of other inorganic materials, 0.5-12% of a polymeric dispersant, and the balance a solvent. In the method, a nano-inorganic material enters a solution composed of the polymeric dispersant and the solvent by means of high speed dispersion according to a predetermined proportion, and after ball milling, the composite nano-powder slurry can be obtained. The composite nano-powder slurry can be applied in antibacterial coatings, deodorants, textiles, paper products, plastics, rubbers, water treatment agents, ship protective agents, cosmetics and other aspects.
Description
Technical Field
The invention relates to the field of antibacterial materials, in particular to high-efficiency environment-friendly antibacterial mildew-proof inorganic composite nano powder slurry obtained by compounding nano magnesium oxide and other nano inorganic substances and a preparation method thereof.
Background
The breeding of bacteria and mould in the living environment and some articles of people not only harms the human health, but also pollutes the environment and damages the articles. Therefore, the research and application of the high-efficiency environment-friendly antibacterial mildew inhibitor have very important significance for protecting human health and improving living environment. Most of traditional antibacterial agents are organic antibacterial agents which are high in sterilization speed and mature in development and use technologies, but have the defects of toxicity of different degrees, irritation to skin, unpleasant odor, volatility, short drug effect, incapability of broad-spectrum sterilization, complex operation, large one-time investment and the like.
Disclosure of Invention
The invention aims to provide the inorganic composite nano powder slurry which is obtained by compounding inorganic substances such as nano magnesium oxide and the like, has high efficiency, long-acting antibiosis, mould prevention and environmental protection, and has the advantages of simple preparation method operation, easy control of process conditions and low cost.
The technical scheme of the invention is as follows:
an efficient, environment-friendly, antibacterial and mildewproof inorganic composite nano powder slurry is a suspension liquid consisting of a nano inorganic substance, a macromolecular dispersant and a solvent, and a highly uniform dispersion system is formed after dispersion and grinding; the nano-magnesia is taken as a main body, and is compounded with one or more than one inorganic substances of nano-zinc oxide, nano-titanium oxide, nano-copper oxide, nano-cuprous oxide, nano-silver oxide, nano-zinc sulfide, nano-zirconium oxide, nano-yttrium oxide, nano-aluminum oxide, nano-calcium oxide and the like to form nano-powder slurry. The nano-powder slurry contains 0.1-40% (preferably 1-30%) of nano-magnesia, 0.01-40% (preferably 0.03-30%) of other inorganic substances, 0.5-12% (preferably 1-8%) of a polymeric dispersant and the balance of a solvent in percentage by weight.
The preparation method of the high-efficiency environment-friendly antibacterial mildew-proof inorganic composite nano powder slurry utilizes a high dispersion system formed by nano magnesium oxide and one or more than one nano inorganic substances in a solution composed of a macromolecular dispersant and a solvent to prepare a series of inorganic composite nano powder slurries. The method comprises the steps of taking magnesium oxide powder with the average particle size of less than 100nm and one or more than one nano inorganic matters with the average particle size of less than 100nm as raw materials, dispersing the raw materials into a solution composed of a polymer dispersing agent and a solvent at a high speed according to a preset proportion, wherein the dispersing speed is 400-3000 rpm (preferably 500-2500 rpm), the dispersing time is 2-120 min (preferably 5-60), and performing ball milling on the mixture for 20-20 h (preferably 40-15 h) to form highly dispersed inorganic composite nano powder slurry. The ball milling mode of the mixture is a planetary, roller or vibration ball milling method.
The macromolecular dispersant is one or more compounds selected from polyolefins, polycarboxylic acids, polycarboxylic acid salts, polyacrylic acids, polyacrylic acid salts, polyesters, polyester salts, polyamides, polyamide salts, polyurethanes, polyurethane salts, polyethers, polyether salts, polyanhydrides, polysiloxanes, polyoxyethylenes, polyoxypropylenes, maleic anhydrides, polyepsilon-caprolactone, polyols and alcohols.
Wherein the solvent is one or more compounds selected from aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, alcohols, ketones, esters, terpenes, alcohol ethers and ether esters, substituted hydrocarbon, and water.
In the invention, the antibacterial mechanism of the nano inorganic substance is as follows:
(1) nano magnesium oxide
Magnesium oxide is very easy to hydrate, a layer of magnesium hydroxide is formed on the surface, and oxygen dissolved in the solution generates active oxygen ions through a single-electron reduction reaction. The surface of the magnesium oxide is coated with a layer of hydroxide ions, and because oxygen has chemical stability in an alkaline environment, high-concentration active oxygen ions exist on the surface of the magnesium oxide. The active oxygen ions have strong oxidizability and can destroy peptide bond structures of cell membrane walls of bacteria, so that the bacteria are killed quickly. In addition, the nano magnesium oxide particles may generate destructive adsorption and may also destroy the cell membrane of bacteria. The antibacterial mechanism can overcome the defects that the silver antibacterial agent has slow action and is easy to discolor and the titanium dioxide antibacterial agent needs ultraviolet irradiation.
(2) Nano zinc oxide
Under the illumination condition, the antibiosis of the nano zinc oxide is the result of the combined action of photocatalysis and metal ion dissolution, and the antibacterial property of the nano zinc oxide to staphylococcus aureus is stronger than that of escherichia coli because the staphylococcus aureus has more negative charges in a near-neutral or slightly alkaline environment, and the nano zinc oxide with positive charges is easier to adsorb to the surface of the staphylococcus aureus, thereby killing the staphylococcus aureus; in the absence of illumination, only the metal ion dissolution mechanism is in effect, and the smaller the particle size of the nanoparticles, the stronger the photocatalytic effect.
(3) Nano titanium oxide
Due to TiO2The electronic structure has the characteristics that superoxide anion free radicals and hydroxyl free radicals with strong chemical activity are generated when the electronic structure receives light, organic matters are attacked, and the effect of degrading organic pollutants is achieved. When encountering bacteria, the bacteria directly attack the cells of the bacteria, so that organic matters in the bacteria cells are degraded, thereby killing the bacteria and decomposing the bacteria. The commonly used bactericides such as silver and copper can inactivate bacterial cells, but harmful components such as endotoxin are released from corpses after the bacteria are killed. The nano titanium dioxide is a non-dissolution type material, does not decompose or dissolve out, has lasting photocatalytic action and has lasting effects of sterilizing and degrading pollutants.
(4) Nano copper oxide
The nano copper oxide can resist bacteria and fungi, can be easily mixed into plastics, synthetic fibers, adhesives, coatings and the like, can keep high activity for a long time even in a harsh environment, and has better antibacterial effect on staphylococcus aureus and bacillus subtilis.
(5) Nano cuprous oxide
Cuprous oxide is used as a broad-spectrum antibacterial agent with low toxicity, mainly acts by releasing copper ions and-SH, -N2H, -COOH, -OH and other groups in proteins in fungi or bacteria to cause bacterial death, is insoluble in organic solvents and water, and is soluble in dilute inorganic acids (hydrochloric acid, sulfuric acid, nitric acid) and ammonia. The copper oxide is easy to be slowly oxidized into copper oxide in humid air and is stable in dry air.
(6) Nano silver oxide
The silver ions with positive charges released by the nano silver oxide react with the sulfhydryl groups with negative charges in the bacterial protease, and the protease loses activity rapidly due to the loss of the sulfhydryl groups, so that the bacteria can not be split and propagated to be killed. When the thallus loses activity, silver ions are dissociated from the thallus, and the sterilization activity is repeated, so that the antibacterial effect is durable. In addition, silver ions also have a photocatalytic effect. Under the action of light, the silver ions can play a role of catalyzing active centers, activate oxygen in water and air, generate hydroxyl radicals and active oxygen ions, and the active oxygen ions have strong oxidizing capability and can destroy the proliferation capability of bacteria in a short time to kill cells.
(7) Nano zinc sulfide
The antibacterial mechanism of the nano zinc sulfide is that when the nano zinc sulfide contacts with bacteria, zinc ions are slowly released, and because the zinc ions have oxidation-reduction property and can react with organic matters (sulfo groups, carboxyl groups and hydroxyl groups), the zinc ions can be combined with bacterial cell membranes and membrane proteins to damage the structures of the bacterial cell membranes and the membrane proteins, and after entering cells, the zinc ions are combined with enzymes and react with DNA to achieve the antibacterial purpose.
(8) Nano zirconium oxide
The nano zirconia is positively charged nano particles, which have strong adsorption effect on bacteria, so that other particles with antibacterial effect fully act with the bacteria, and the antibacterial effect is enhanced.
(9) Nano yttrium oxide
The nanometer yttrium oxide is positively charged nanometer particle, and has strong adsorption to bacteria, so that other particles with antibacterial effect can fully act with bacteria to strengthen the antibacterial effect.
(10) Nano alumina
The nanometer yttrium oxide is positively charged nanometer particle, and has strong adsorption to bacteria, so that other particles with antibacterial effect can fully act with bacteria to strengthen the antibacterial effect.
(11) Nano calcium oxide
The nano calcium oxide can play an antibacterial role through local strong alkalinity.
The invention has the advantages that:
1. strong antibacterial and mildew-proof performance. The inorganic composite nano powder slurry prepared by the method has the synergistic antibacterial and mildewproof performance of various inorganic substances and has a synergistic effect, and the antibacterial effect of the inorganic composite nano powder slurry is far higher than that of a single nano powder slurry with the same concentration.
2. Simple process and low cost. The invention adopts a method of combining dispersion and ball milling to prepare the inorganic composite nano-powder slurry, and the process and the equipment are mature and simple.
3. Has high dispersibility. The inorganic composite nano-powder slurry prepared by the technology forms a highly dispersed system, can be uniformly dispersed in other systems, has the storage period of more than one year, has excellent antibacterial and antifungal properties, reaches or exceeds the international advanced level, has potential wide application prospect in the aspects of antibacterial coatings, deodorants, textiles, paper products, plastics, rubber, water treatment agents, ship protective agents and the like, and is an inorganic antibacterial agent with great use value.
4. The inorganic antibacterial agent has the excellent performances of long-acting, environmental protection, high antibacterial rate and the like, and the inorganic antibacterial agents such as nano-scale zinc oxide, titanium oxide, copper oxide, cuprous oxide, silver oxide, zinc sulfide, zirconium oxide, yttrium oxide, aluminum oxide, calcium oxide and the like have different antibacterial mechanisms, and can play the peculiar effects of antibiosis and mildew prevention after being compounded.
Detailed Description
The invention is described in detail by examples, wherein the proportions are weight ratios, the antibacterial performance of the powder is determined according to the national standard GB/T21510-2007 method, and the antibacterial and mildew resistance of the coating is determined according to the HG/T3950-2007 industry standard, except for special indications.
Example 1
840g of deionized water is weighed in a 2000ml beaker, stirred at high speed under the condition of 1000rpm by a high-speed dispersion machine, 60g of a high molecular dispersant (Disperbyk 192 of Bick chemical company, Germany) is added, 70g of magnesium oxide powder with the average particle size of 50nm, 20g of zinc oxide powder and 10g of titanium oxide powder are respectively added for dispersion for 60min, and the mixture is subjected to planetary ball milling for 5h at the rotating speed of 300rpm of a ball mill to form highly dispersed inorganic composite nano powder slurry. According to the original mixture ratio, the weight ratio of the nano magnesium oxide is 7%, the weight ratio of the nano zinc oxide is 2%, the weight ratio of the nano titanium oxide is 1%, the total weight ratio of the composite powder is 10%, and the weight ratio of the polymer dispersant is 6%.
The inorganic composite nano-powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 99.2 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 99.96 percent within 24 hours. The inorganic composite nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.93 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 1 grade.
Example 2
700g of deionized water is weighed in a 2000ml beaker, high-speed stirring is carried out by a high-speed dispersion machine under the condition of 2000rpm, 100g of a high molecular dispersing agent (Disperbyk 192 of Bick chemical company, Germany) is added, 40g of magnesium oxide powder with the average particle size of 60nm, 120g of zinc oxide powder and 40g of titanium oxide powder are respectively added, dispersion is carried out for 120min, the mixture is subjected to planetary ball milling for 10h, and the rotating speed of a ball mill is 500rpm, so as to form highly dispersed inorganic composite nano powder slurry. According to the original mixture ratio, the weight ratio of the nano magnesium oxide is 4%, the weight ratio of the nano zinc oxide is 12%, the weight ratio of the nano titanium oxide is 4%, the total weight ratio of the composite powder is 20%, and the weight ratio of the polymer dispersant is 10%.
The inorganic composite nano-powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 99.3 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 99.99 percent within 24 hours. The inorganic composite nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.96 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 0 grade.
Example 3
890g of deionized water is weighed in a 2000ml beaker, stirred at a high speed under the condition of 500rpm by a high-speed dispersion machine, 30g of a high molecular dispersing agent (Disperbyk 192 of Bick chemical company, Germany) is added, 40g of magnesium oxide powder with the average particle size of 30nm and 40g of zinc oxide powder are respectively added, the mixture is dispersed for 10min, and the mixture is subjected to vibration ball milling for 2h to form highly dispersed inorganic composite nano powder slurry. According to the original proportion, the weight ratio of the nano magnesium oxide is 4%, the weight ratio of the nano zinc oxide is 4%, the total weight ratio of the composite powder is 8%, and the weight ratio of the polymer dispersant is 3%.
The inorganic composite nano-powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 99.5 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 99.94 percent within 24 hours. The inorganic composite nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.93 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 1 grade.
Example 4
900g of deionized water is weighed in a 2000ml beaker, stirred at high speed under the condition of 700rpm by a high-speed dispersion machine, 50g of a high molecular dispersing agent (Disperbyk 192 of Bick chemical company, Germany) is added, 45g of magnesium oxide powder with the average particle size of 80nm and 5g of titanium oxide powder are respectively added, the mixture is dispersed for 40min, and the mixture is ball-milled for 15h by a roller type to form highly dispersed inorganic composite nano powder slurry. According to the original proportion, the weight ratio of the nano magnesium oxide is 4.5%, the weight ratio of the nano titanium oxide is 0.5%, the total weight ratio of the composite powder is 5%, and the weight ratio of the polymer dispersant is 5%.
The inorganic composite nano-powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 99.0 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 99.5 percent within 24 hours. The inorganic composite nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.2 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 1 grade.
Example 5
800g of deionized water is weighed in a 2000ml beaker, stirred at a high speed of 2500rpm by a high-speed dispersion machine, 80g of a high molecular dispersant (Disperbyk 192 of Bick chemical company, Germany) is added, 84g of magnesium oxide powder with the average particle size of 40nm, 24g of zinc oxide powder, 10.8g of titanium oxide powder and 1.2g of copper oxide powder are respectively added, the mixture is dispersed for 100min, and the mixture is subjected to planetary ball milling for 8h at the ball mill rotating speed of 600rpm to form highly dispersed inorganic composite nano powder slurry. According to the original mixture ratio, the weight ratio of the nano magnesium oxide is 8.4%, the weight ratio of the nano zinc oxide is 2.4%, the weight ratio of the nano titanium oxide is 1.08%, the weight ratio of the nano copper oxide is 0.12%, the total weight ratio of the composite powder is 12%, and the weight ratio of the polymer dispersant is 8%.
The inorganic composite nano-powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 99.6 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 99.97 percent within 24 hours. The inorganic composite nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.98 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 0 grade.
Example 6
630g of deionized water is weighed in a 2000ml beaker, stirred at a high speed of 3000rpm by a high-speed dispersion machine, 120g of a high molecular dispersant (Disperbyk 192 of Bick chemical company, Germany) is added, 75g of magnesium oxide powder with the average particle size of 20nm, 100g of zinc sulfide, 73.75g of titanium oxide and 1.25g of cuprous oxide are respectively added, and the mixture is dispersed for 110min, and is subjected to vibration ball milling for 6h to form highly dispersed inorganic composite nano powder slurry. According to the original mixture ratio, the weight ratio of the nano-magnesia is 7.5%, the weight ratio of the nano-zinc sulfide is 10%, the weight ratio of the nano-titanium oxide is 7.375%, the weight ratio of the nano-cuprous oxide is 0.125%, the total weight ratio of the composite powder is 25%, and the weight ratio of the polymer dispersant is 12%.
The inorganic composite nano-powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 99.7 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 99.98 percent within 24 hours. The inorganic composite nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.98 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 0 grade.
Example 7
780g of deionized water is weighed in a 2000ml beaker, stirred at high speed under the condition of 1500rpm by a high-speed dispersion machine, 70g of a high molecular dispersing agent (Disperbyk 192 of Bick chemical company, Germany) is added, 148.5g of magnesium oxide powder with the average particle size of 45nm and 1.5g of silver oxide powder are respectively added, the mixture is dispersed for 80min, and the mixture is ball-milled for 13h by a roller type to form highly dispersed inorganic composite nano powder slurry. According to the original mixture ratio, the weight ratio of the nano magnesium oxide is 14.85%, the weight ratio of the nano silver oxide is 0.15%, the total weight ratio of the composite powder is 15%, and the weight ratio of the polymer dispersant is 7%.
The inorganic composite nano-powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 98.9 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 99.96 percent within 24 hours. The inorganic composite nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.94 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 0 grade.
Example 8
730g of deionized water is weighed in a 2000ml beaker, stirred at a high speed of 1800rpm by a high-speed dispersion machine, 90g of a high molecular dispersant (Disperbyk 192 of Bick chemical company, Germany) is added, 140g of magnesium oxide powder with the average particle size of 85nm, 25g of zinc sulfide powder, 10g of alumina powder and 10g of calcium oxide powder are respectively added, the mixture is dispersed for 30min, and the mixture is subjected to planetary ball milling for 7h at the rotating speed of 450rpm of the ball mill to form highly dispersed inorganic composite nano powder slurry. According to the original mixture ratio, the weight ratio of the nano magnesium oxide is 13.9%, the weight ratio of the nano zinc sulfide is 2.49%, the weight ratio of the nano aluminum oxide is 1%, the weight ratio of the nano calcium oxide is 1%, the total weight ratio of the composite powder is 18.4%, and the weight ratio of the polymer dispersant is 8.96%.
The inorganic composite nano-powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 98.3 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 99.90 percent within 24 hours. The inorganic composite nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.8 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 1 grade.
Example 9
490g of deionized water is weighed in a 2000ml beaker, stirred at high speed under the condition of 1300rpm by a high-speed dispersion machine, 110g of a high molecular dispersing agent (Disperbyk 192 of Bick chemical company, Germany) is added, 40g of magnesium oxide powder with the average particle size of 70nm, 320g of zinc oxide, 20g of zirconium oxide, 20g of yttrium oxide and 8g of silver oxide are respectively added, the mixture is dispersed for 90min, and the mixture is subjected to planetary ball milling for 12h at the ball mill rotating speed of 350rpm to form highly dispersed inorganic composite nano powder slurry. According to the original mixture ratio, the weight ratio of the nano magnesium oxide is 3.97%, the weight ratio of the nano zinc oxide is 31.7%, the weight ratio of the nano zirconium oxide is 1.98%, the weight ratio of the nano yttrium oxide is 1.98%, the weight ratio of the nano silver oxide is 7.94%, the total weight ratio of the composite powder is 40.5%, and the weight ratio of the polymer dispersant is 10.9%.
The inorganic composite nano-powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 99.4 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 99.98 percent within 24 hours. The inorganic composite nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.99 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 0 grade.
Example 10
780g of deionized water is weighed in a 2000ml beaker, stirred at high speed under the condition of 400rpm by a high-speed dispersion machine, 60g of a high molecular dispersing agent (Disperbyk 192 of Bick chemical company, Germany) is added, 96g of magnesium oxide powder with the average particle size of 25nm, 48g of zinc oxide, 12.8g of calcium oxide, 1.6g of silver oxide and 1.6g of copper oxide are respectively added, the mixture is dispersed for 120min, and the mixture is subjected to planetary ball milling for 20min, wherein the rotating speed of the ball mill is 800rpm, so that highly dispersed inorganic composite nano powder slurry is formed. According to the original mixture ratio, the weight ratio of the nano magnesium oxide is 9.6%, the weight ratio of the nano zinc oxide is 4.8%, the weight ratio of the nano calcium oxide is 1.28%, the weight ratio of the nano silver oxide is 0.16%, the weight ratio of the nano copper oxide is 0.16%, the total weight ratio of the composite powder is 16%, and the weight ratio of the polymeric dispersant is 6%.
The inorganic composite nano-powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 99.3 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 99.96 percent within 24 hours. The inorganic composite nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.98 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 0 grade.
Example 11
The solvent in the example 1 is changed from 840g of water to 672g of petroleum ether and 168g of trichloroethane, and the dispersant adopts Anti-Terra-202 of Bick chemical company of Germany, but the added weight ratio is not changed, and the amount of other substances and the process parameters are not changed, so that the inorganic composite nano-powder slurry is prepared.
The inorganic composite nano powder slurry is added into the paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.80 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 1 grade.
Example 12
Will be as in example 2The solvent is changed from 700g of water to 380g of xylene and 320g of toluene, and the dispersant is TEXAPHOR from Henkel of Hegham
963S, and preparing the inorganic composite nano powder slurry, wherein the added weight ratio is unchanged, and the amount of other substances and process parameters are unchanged.
The inorganic composite nano powder slurry is added into the paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.93 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 0 grade.
Example 13
The solvent in example 3 was changed from 890g of water to 840g of isohexane and 50g of turpentine, and the dispersant was Hypersol L4708 from Danish KVK company, but the added weight ratio was not changed, and the amount of other substances and process parameters were not changed, to prepare inorganic composite nanopowder slurry.
The inorganic composite nano powder slurry is added into the paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.88 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 1 grade.
Example 14
The solvent in example 4 was changed from 900g of water to 900g of isopropanol, and the dispersant used was Solsperse41090 from Avecia, Germany, but the added weight ratio was unchanged, and the amounts of other materials and process parameters were unchanged, to prepare an inorganic composite nanopowder slurry.
The inorganic composite nano powder slurry is added into the paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.30 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 1 grade.
Example 15
The solvent in example 5 was changed from 800g of water to 800g of cyclohexanone, and the dispersant used was TEXAPHOR from Henkel, Hangao
3250, however, addingThe weight ratio is unchanged, the amount of other substances and the process parameters are unchanged, and the inorganic composite nano-powder slurry is prepared.
The inorganic composite nano powder slurry is added into the paint with the powder content of 1 percent by weight, the antibacterial rate of the composite nano antibacterial paint reaches 99.95 percent in 24 hours, the antibacterial rate is I grade, and the mildew grade is 0 grade.
Comparative example 1
Pure nano-magnesia aqueous slip was prepared using the same process parameters as in example 1, with a final nano-magnesia weight ratio of 10%.
The nano powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 62.2 percent in 1 hour, and the sterilization rate of Escherichia coli reaches 93.6 percent in 24 hours. The inorganic nano powder slurry is added into acrylic acid water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the nano antibacterial paint reaches 95 percent in 24 hours, the nano antibacterial paint is II grade, and the mildew grade is 2 grade.
Comparative example 2
Pure magnesium oxide aqueous slurry was prepared by using the same process parameters as in example 1, the particle size of magnesium oxide was 1 to 100 μm, and the final magnesium oxide weight ratio was 10%.
The powder slurry is added into Nutrient Broth (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 22 percent in 1 hour, and the sterilization rate of Escherichia coli reaches 28 percent in 24 hours. The inorganic powder slurry is added into acrylic acid water-based paint according to the weight percentage of 1 percent of the powder content, the antibacterial rate of the 24-hour antibacterial paint reaches 31 percent, and the antibacterial paint basically has no mildew resistance.
Comparative example 3
Pure nano-magnesia slurries were prepared with the same process parameters as in example 11, with a final nano-magnesia weight ratio of 10%.
The inorganic nano powder slurry is added into the coating with the powder content of 1 percent by weight, the antibacterial rate of the nano antibacterial coating reaches 94.4 percent in 24 hours, the nano antibacterial coating is II grade, and the mildew grade is 2 grade.
Comparative example 4
Pure nano zinc oxide aqueous slurry was prepared by using the same process parameters as in example 1, and the final nano zinc oxide weight ratio was 10%.
The nano powder slurry is added into a nutrient broth culture medium (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 88.0 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 95.1 percent within 24 hours. The inorganic nano powder slurry is added into acrylic water-based paint with the powder content of 1 percent by weight, the antibacterial rate of the nano antibacterial paint reaches 96.5 percent in 24 hours, the nano antibacterial paint is II grade, and the mildew grade is 2 grade.
Comparative example 5
Pure zinc oxide aqueous slurry is prepared by adopting the same process parameters as the example 1, the granularity of the zinc oxide is between 1 and 100 mu m, and the final weight ratio of the zinc oxide is 10 percent.
The powder slurry is added into Nutrient Broth (NB) with the powder content of 0.5 percent by weight, the sterilization rate of Escherichia coli reaches 25 percent within 1 hour, and the sterilization rate of Escherichia coli reaches 31 percent within 24 hours. The inorganic powder slurry is added into acrylic acid water-based paint according to the weight percentage of 1 percent of the powder content, the antibacterial rate of the 24-hour antibacterial paint reaches 33 percent, and the antibacterial paint basically has no mildew resistance.
Comparative example 6
Pure nano-zinc oxide slip was prepared using the same process parameters as in example 11, with a final nano-zinc oxide weight ratio of 10%.
The inorganic nano powder slurry is added into the coating with the powder content of 1 percent by weight, the antibacterial rate of the nano antibacterial coating reaches 96.0 percent in 24 hours, the nano antibacterial coating is II grade, and the mildew grade is 2 grade.
As can be seen from the examples and comparative examples, the inorganic composite nano-powder slurry prepared by the method of the invention has excellent antibacterial and mildewproof effects.
Claims (4)
1. The high-efficiency environment-friendly antibacterial mildew-proof inorganic composite nano powder slurry is characterized in that: the inorganic composite nano powder slurry is a suspension consisting of a nano inorganic substance, a high molecular dispersant and a solvent, and a uniform dispersion system is formed after dispersion and grinding; wherein,
7.5 percent of nano magnesium oxide, 10 percent of nano zinc sulfide, 7.375 percent of nano titanium oxide, 0.125 percent of nano cuprous oxide, 25 percent of composite powder, 12 percent of polymer dispersant and the balance of solvent;
or the weight ratio of the nano magnesium oxide is 13.9 percent, the weight ratio of the nano zinc sulfide is 2.49 percent, the weight ratio of the nano aluminum oxide is 1 percent, the weight ratio of the nano calcium oxide is 1 percent, the total weight ratio of the composite powder is 18.4 percent, the weight ratio of the polymer dispersant is 8.96 percent, and the balance is solvent;
or the weight ratio of the nano magnesium oxide is 3.97%, the weight ratio of the nano zinc oxide is 31.7%, the weight ratio of the nano zirconium oxide is 1.98%, the weight ratio of the nano yttrium oxide is 1.98%, the weight ratio of the nano silver oxide is 7.94%, the total weight ratio of the composite powder is 40.5%, the weight ratio of the polymeric dispersant is 10.9%, and the balance is solvent;
the average particle size of the nano magnesium oxide is less than 100nm, the average particle size of the nano zinc oxide is less than 100nm, the average particle size of the nano titanium oxide is less than 100nm, the average particle size of the nano cuprous oxide is less than 100nm, the average particle size of the nano silver oxide is less than 100nm, the average particle size of the nano zinc sulfide is less than 100nm, the average particle size of the nano zirconium oxide is less than 100nm, the average particle size of the nano yttrium oxide is less than 100nm, the average particle size of the nano aluminum oxide is less than 100nm, and the average particle size of the nano calcium oxide is less than 100 nm;
the macromolecular dispersant is one or more compounds selected from polyolefins, polycarboxylic acids, polycarboxylate, polyacrylic acids, polyacrylate, polyesters, polyester salts, polyamides, polyamide salts, polyurethanes, polyurethane salts, polyethers, polyether salts, polyanhydrides, polysiloxanes, polyoxyethylenes, polyoxypropylenes, maleic anhydrides, polyepsilon-caprolactone, polyols and alcohols;
the solvent is one or more compounds selected from aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, alcohol, ketone, ester, terpenes, alcohol ether and ether ester, substituted hydrocarbon and water.
2. The preparation method of the high-efficiency environment-friendly antibacterial mildewproof inorganic composite nano-powder slurry according to claim 1, which is characterized by comprising the following steps of: preparing inorganic composite nano powder slurry of a series of components by utilizing a dispersion system formed by nano magnesium oxide and one or more than one nano inorganic substance in a solution composed of a macromolecular dispersant and a solvent; the method comprises the steps of taking magnesium oxide powder with the average particle size of less than 100nm and one or more than one nano inorganic matters with the average particle size of less than 100nm as raw materials, dispersing the raw materials into a solution composed of a high molecular dispersing agent and a solvent at a high speed according to a preset proportion, wherein the dispersing speed is 400-3000 rpm, the dispersing time is 2-120 min, and performing ball milling on the mixture for 20 min-20 h to form highly dispersed inorganic composite nano powder slurry.
3. The preparation method of the high-efficiency environment-friendly antibacterial mildewproof inorganic composite nano-powder slurry according to claim 2, which is characterized by comprising the following steps of: the preferred dispersing speed is 500-2500 rpm, the preferred dispersing time is 5-60 min, and the preferred ball milling time of the mixture is 40-15 h, so that the highly dispersed inorganic composite nano-powder slurry is formed.
4. The preparation method of the high-efficiency environment-friendly antibacterial mildewproof inorganic composite nano-powder slurry according to claim 2, which is characterized by comprising the following steps of: the ball milling mode of the mixture is a planetary, roller or vibration ball milling method.
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| CN115119850A (en) * | 2022-07-11 | 2022-09-30 | 浙江新安化工集团股份有限公司 | Compound mildew-proof antibacterial agent, preparation method thereof, long-acting mildew-proof alcohol-type sealant and preparation method thereof |
| CN116004103A (en) * | 2023-01-12 | 2023-04-25 | 上海大学 | Antibacterial flame-retardant coating based on copper oxide-polymer composite material and preparation method and application thereof |
| CN116288203B (en) * | 2023-03-10 | 2024-07-19 | 昆明理工大学 | Corrosion-resistant antibacterial biomedical composite coating and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412251A (en) * | 2001-10-12 | 2003-04-23 | 中国科学院金属研究所 | Nano zinc oxide slurry composition and its preparation method |
| CN1450124A (en) * | 2002-04-10 | 2003-10-22 | 中国科学院金属研究所 | Nano zircon oxide slurry composition and preparation process thereof |
| CN1513924A (en) * | 2003-05-30 | 2004-07-21 | 中国科学院金属研究所 | Nano-aluminium oxide paste composition and its preparation method |
| CN1923927A (en) * | 2005-11-02 | 2007-03-07 | 中科纳米涂料技术(苏州)有限公司 | Nano composite normal temperature type gage mark coating and preparation method thereof |
| WO2009111393A2 (en) * | 2008-03-05 | 2009-09-11 | Applied Nanotech Holdings, Inc. | Additives and modifiers for solvent- and water-based metallic conductive inks |
| CN101649131A (en) * | 2008-08-15 | 2010-02-17 | 富港电子（东莞）有限公司 | Composite nano-coating, preparation method and application thereof |
| CN102181206A (en) * | 2011-04-21 | 2011-09-14 | 浙江海洋学院 | Antifouling paint containing nano oxides |
-
2011
- 2011-12-06 CN CN201110401227.3A patent/CN102511503B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412251A (en) * | 2001-10-12 | 2003-04-23 | 中国科学院金属研究所 | Nano zinc oxide slurry composition and its preparation method |
| CN1450124A (en) * | 2002-04-10 | 2003-10-22 | 中国科学院金属研究所 | Nano zircon oxide slurry composition and preparation process thereof |
| CN1513924A (en) * | 2003-05-30 | 2004-07-21 | 中国科学院金属研究所 | Nano-aluminium oxide paste composition and its preparation method |
| CN1923927A (en) * | 2005-11-02 | 2007-03-07 | 中科纳米涂料技术(苏州)有限公司 | Nano composite normal temperature type gage mark coating and preparation method thereof |
| WO2009111393A2 (en) * | 2008-03-05 | 2009-09-11 | Applied Nanotech Holdings, Inc. | Additives and modifiers for solvent- and water-based metallic conductive inks |
| CN101649131A (en) * | 2008-08-15 | 2010-02-17 | 富港电子（东莞）有限公司 | Composite nano-coating, preparation method and application thereof |
| CN102181206A (en) * | 2011-04-21 | 2011-09-14 | 浙江海洋学院 | Antifouling paint containing nano oxides |
Non-Patent Citations (4)
| Title |
|---|
| 徐丽丽，等.纳米二氧化钛抗菌材料的研究与应用进展.《山东陶瓷》.2007,第30卷(第5期),26-29. * |
| 李一凌.纳米抗菌材料应用研究进展.《科技创新导报》.2009,(第3期),1. |
| 纳米抗菌材料应用研究进展;李一凌;《科技创新导报》;20090131(第3期);1 * |
| 郑典模,等.纳米MgO改性涂料的制备及其抗菌性能研究.《南昌大学学报·工科版》.2007,第29卷(第4期),315-322. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11834775B2 (en) | 2018-10-16 | 2023-12-05 | Imam Abdulrahman Bin Faisal University | Antimicrobial fabric manufacturing method |
| US12098500B2 (en) | 2023-10-20 | 2024-09-24 | Imam Abdulrahman Bin Faisal University | Method for making an antimicrobial cotton textile |
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