CN111436459B - Inorganic mildew-proof antibacterial material, preparation method and application thereof, and inorganic mildew-proof antibacterial liquid - Google Patents
Inorganic mildew-proof antibacterial material, preparation method and application thereof, and inorganic mildew-proof antibacterial liquid Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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- A—HUMAN NECESSITIES
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Abstract
The invention belongs to the technical field of mildew resistance and antibiosis, and particularly relates to an inorganic mildew-resistant antibacterial material, and a preparation method and application thereof. The inorganic mildew-proof antibacterial material provided by the invention is doped magnesium silicate or a doped magnesium silicate derivative with a chemical formula of Nak(Si8Mgx(AyBz)O20(OH)mRn)·tH2And O. The invention synthesizes the inorganic mildew-proof antibacterial material similar to natural ore for the first time. The material can be used as a mildew-proof antibacterial agent, and the aqueous solution prepared from the material is transparent, so that the use requirement of scenes with mildew-proof antibacterial requirements of transparent coatings can be met.
Description
Technical Field
The invention belongs to the technical field of mildew resistance and antibiosis, and particularly relates to an inorganic mildew-resistant antibacterial material, and a preparation method and application thereof.
Background
With the improvement of living standard of people, the increase of garbage of various food articles inevitably brings good living environment for bacteria and mould. The traditional transparent mildew-proof antibacterial agent forms a stable aqueous solution system through complexation, so that certain hidden danger is brought to the stability of later-stage materials, some materials have the risk of difficult degradation and have the killing effect on beneficial bacteria and algae organisms in the environment, and thus, many countries propose forbidden laws for using inorganic mildew-proof materials.
In order to overcome some defects caused by the traditional inorganic transparent mildew-proof antibacterial material, the technology utilizes an artificial synthesis method of natural material magnesium silicate and derivatives thereof to prepare magnesium silicate containing silver, zinc, copper, cobalt and nickel and derivatives thereof, and the materials are dispersed in water to form transparent mildew-proof antibacterial solution.
Disclosure of Invention
In order to overcome the defects of the existing inorganic transparent antibacterial mildew-proof material, the invention provides a method for artificially synthesizing natural magnesium silicate and derivatives thereof, which are used for preparing magnesium silicate containing silver, zinc, copper and nickel and derivatives thereof, and the materials are dispersed in water to form transparent antibacterial mildew-proof solution.
The technical scheme provided by the invention is as follows:
an inorganic mildew-proof antibacterial material is doped magnesium silicate or a doped magnesium silicate derivative.
The inventors of the present invention have found that magnesium silicate or a magnesium silicate derivative can be modified by doping with magnesium silicate or a magnesium silicate derivative, thereby imparting a mold-proofing and antibacterial function to magnesium silicate or a magnesium silicate derivative.
Specifically, the magnesium silicate is doped with cations and/or anions.
Based on the technical scheme, the magnesium silicate can be functionally modified by doping of cation doping, and the electronegativity of the material can be changed and the transparency function can be improved by doping of anion.
Specifically, the doping of the magnesium silicate derivative is cation doping and/or anion doping.
Based on the technical scheme, the magnesium silicate derivative can be functionally modified by doping with cations, and the electronegativity of the material can be changed, the transparency can be improved, and the thixotropy of the material can be modified by doping with anions.
In particular, the cationic doping of the magnesium silicate is a doping of antibacterial cations and/or modified cations.
Based on the technical scheme, the antibacterial function can be realized by doping the antibacterial cations, and the functions of adjusting the material layer spacing, changing the thixotropy of the material, improving the mildew-proof antibacterial activity by changing the space structure of the material and the hole potential can be realized by doping the modified cations.
In particular, the cation doping of the magnesium silicate derivative is the doping of an antibacterial cation and/or a modified cation.
Based on the technical scheme, the antibacterial function can be realized by doping the antibacterial cations, and the functions of adjusting the material layer spacing, changing the thixotropy of the material, improving the mildew-proof antibacterial activity by changing the space structure of the material and the hole potential can be realized by doping the modified cations.
Specifically, the magnesium silicate derivative is lithium magnesium silicate, magnesium aluminum silicate, magnesium fluorosilicate, lithium magnesium fluorosilicate or magnesium aluminum fluorosilicate.
Specifically, the chemical formula of the inorganic mildew-proof antibacterial material is Nak(Si8Mgx(AyBz)O20(OH)mRn)·tH2O, wherein:
a is antibacterial cation, and is selected from one or more of Zn, N i, Cu, Co or Ag;
b is a modified cation, B is selected from L i, Na, K, Al, Ca, T i, V, Cr, Mn, Fe, Ge, Sn or NH4 +Any one or more of;
r is selected from any one or more of C-containing anionic groups, F-containing anionic groups, As-containing anionic groups, P-containing anionic groups or B-containing anionic groups;
k is more than or equal to 0 and less than 1; 4< x + y + z <7, and 0-5 of y + z; m + n is less than or equal to 4; t is the amount of bound water 0< t <8, corresponding to a bound water amount of 15% by mass or less.
Specifically, Li, Na, K, Al, Ca, Ti, V, Cr, Mn, Fe, Ge, Sn or NH4 +In (1).
The technical scheme provides the chemical composition of the inorganic mildew-proof antibacterial material.
Further, the silver inorganic mildew-proof antibacterial material can be in different colors according to the preparation conditions, as shown in fig. 2.
The invention also provides a preparation method of the inorganic mildew-proof antibacterial material, which comprises the following steps: the inorganic mildew-proof antibacterial material is prepared by a hydrothermal synthesis method.
The preparation method is mature in technology, easy to realize and easy for industrial production.
Specifically, the preparation method of the inorganic mildew-proof antibacterial material comprises the following steps:
the method comprises the following steps:
1) mixing a magnesium-containing compound, a silicon-containing compound and a compound containing a mildew-proof antibacterial element according to a metering ratio, adjusting the pH to 7-13, and reacting for 0.1-48h at the temperature of 0-120 ℃ to obtain an inorganic mildew-proof antibacterial precursor;
or mixing a magnesium-containing compound, a silicon-containing compound, a compound containing the mildew-proof antibacterial element and a modified compound according to a metering ratio, adjusting the pH to 7-13, and reacting for 0.1-48h at the temperature of 0-120 ℃ to obtain an inorganic mildew-proof antibacterial precursor;
2) and (2) reacting the inorganic mildew-proof antibacterial precursor obtained in the step 1) at high temperature and high pressure, wherein the reaction temperature is 120-350 ℃, the reaction time is 0.1-72h, cooling after the reaction is finished, removing redundant impurities, and drying to obtain the inorganic mildew-proof antibacterial material.
The technical scheme provides a specific preparation method of the doped magnesium silicate and the doped magnesium silicate derivative.
Specifically, the magnesium-containing compound is selected from one or more of magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium acetate, magnesium carbonate, basic magnesium carbonate, magnesium oxide and magnesium hydroxide.
Specifically, the silicon-containing compound is selected from any one or a mixture of more of sodium silicate, lithium silicate, potassium silicate, sodium fluorosilicate, potassium fluorosilicate, magnesium fluorosilicate, silicon dioxide and silica sol.
Specifically, the mildew-proof antibacterial element is selected from any one or a mixture of more of silver, copper, zinc, nickel and cobalt elements.
Specifically, the modification compound is one or more selected from lithium salt compounds, sodium salt compounds, potassium salt compounds, aluminum salt compounds, calcium salt compounds, titanium salt compounds, vanadium salt compounds, chromium salt compounds, manganese salt compounds, iron salt compounds, germanium salt compounds, tin salt compounds, ammonium salt compounds and urea.
Specifically, the metering ratio of the silicon-containing compound, the magnesium-containing compound, the mildew-proof antibacterial element and the modified compound is as follows: 8: 2-7: 0-1: 0-5, the metering ratio of the mildew-proof antibacterial elements is greater than or equal to zero, and the metering ratio of the modified compound is greater than or equal to zero.
The technical scheme provides raw materials and the metering ratio of the raw materials of the inorganic mildew-proof antibacterial material provided by the invention.
The invention also provides the application of the inorganic mildew-proof antibacterial material as an inorganic mildew-proof antibacterial agent; or as a nutritional agent.
As shown in fig. 4 and 5, the inorganic anti-mold and anti-bacterial agent provided by the invention has good anti-mold and anti-bacterial functions.
Furthermore, the inorganic mildew-proof antibacterial material provided by the invention is prepared into an aqueous solution or an organic solution, so that a medicament with mildew-proof and antibacterial functions can be obtained, and the medicament is used for producing the mildew-proof and antibacterial functions of articles for daily use and preventing and treating plant germ infection; can also be made into microelement nutrient for supplementing animal and plant microelements. And moreover, as the material can be absorbed and degraded by plants in nature, impurities are not polluted in the environmental safety hazard. .
The invention also provides an inorganic mildew-proof antibacterial liquid which is an aqueous solution or an organic solvent solution of the inorganic mildew-proof antibacterial material. The inorganic mildew-proof antibacterial liquid is a transparent solution, and is shown in figures 1 and 2. The inorganic mildew-proof antibacterial material is in powder or block shape.
The inorganic mildew-proof antibacterial liquid provided by the technical scheme has good mildew-proof and antibacterial effects. As shown in figure 3, the compound has good inhibition effect on both mould and bacteria through experimental detection. The antibacterial and mildewproof antibacterial liquid has good transparency, and can be applied to scenes with the requirement on the transparency of the antibacterial and mildewproof liquid, for example, the antibacterial and mildewproof liquid is suitable for decoration after molding and the mildewproof of glass.
Specifically, the organic solvent may be selected from methanol, ethanol, isopropanol or ethylene glycol.
Further, the content of the inorganic mildew-proof antibacterial material is 0-10 wt%, and 0 wt% is not included.
The inorganic mildew-proof antibacterial material provided by the invention has the following advantages:
1) the material has the crystal structure of natural ore, so that the application and further development are facilitated based on the existing knowledge;
2) the material has certain alkalinity, can be stably and purely used in an alkaline environment, does not change at all, and effectively solves the problem of color change and deterioration caused by the organic antibacterial mildew preventive;
3) the elemental composition of the material is beneficial to the growth of algae plants, can be absorbed and degraded by the plants in nature, and is impure to the problem of potential safety hazard of the environment.
4) The material is relatively stable, and even if the material is dissolved under an acidic condition, the mildew-proof antibacterial ions can generate corresponding silicate precipitates, so that the harm of free metal ions to the environment is avoided.
5) The material has strong thixotropic property, and the amount or variety of the viscosity reducer can be selected according to the use requirement environment to regulate and control the viscosity of the system.
6) The material has the characteristics of safety and no toxicity, and is expected to be used for the preservation of vegetables and fruits, the preservation of various daily necessities and the prevention and treatment of plant germs.
The invention synthesizes the inorganic mildew-proof antibacterial material similar to natural ore material for the first time. The material can be used as a mildew-proof antibacterial agent, and the prepared aqueous solution is transparent, so that the use requirement of scenes with mildew-proof antibacterial requirements of transparent coatings can be met.
Drawings
FIG. 1 is an optical photograph of the copper, zinc, nickel and cobalt containing antifungal and antibacterial materials synthesized by the present invention and their respective aqueous solutions. Wherein, the water solution of the copper, cobalt, zinc and nickel mildew-proof antibacterial material is transparent solution with various colors.
FIG. 2 is an optical photograph of the silver-containing antifungal and antibacterial materials of the present invention and their respective aqueous solutions. The silver mildew-proof antibacterial material has various colors, is transparent solution with various colors at the early stage after being dissolved in water, and can be changed into colorless transparent solution after being added with the oxidation assistant.
FIG. 3 shows the fresh-keeping effect of the composite material of copper, nickel and copper-nickel on steamed bread. Wherein, the storage condition of the tested sample is that the sample is placed indoors for one year in an open way at normal temperature, and the blank contrast is seriously mildewed.
FIG. 4 is a report of the mildew resistance of a paint film formed by compounding the inorganic copper mildew-resistant antibacterial material obtained in example 1 of the present invention with an emulsion at a concentration of 1 mt%.
Fig. 5 is an antibacterial test report of the silver inorganic mildewproof antibacterial material obtained in example 3 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
1) mixing 0.8M sodium silicate solution, 0.54M magnesium sulfate and 0.05M copper sulfate solution according to a volume ratio of 1:1, uniformly mixing, adjusting the pH value to 8 by using a dilute sulfuric acid solution, maintaining the reaction temperature at 90 ℃, and continuously stirring for 5 hours to obtain an inorganic mildew-proof antibacterial precursor;
2) transferring the inorganic mildew-proof antibacterial precursor obtained in the step 1) into a high-temperature high-pressure reaction kettle, carrying out hydrothermal crystallization at 260 ℃ for 8h, cooling, taking out, washing with water until no sulfate radical remains, and drying to obtain the copper inorganic mildew-proof antibacterial material, wherein the chemical formula is as follows: na (Na)0.6(Si8Mg5.4Cu0.5O20(OH)4)·6H2O。
Example 2:
1) mixing 0.8M fumed silica, 0.2M magnesium oxide, 0.03M nickel sulfate and 0.4M aluminum sulfate according to a volume ratio of 1: 1:1, uniformly mixing, adjusting the pH value to 13 by using a sodium hydroxide solution, maintaining the reaction temperature at 25 ℃, and continuously stirring for 36 hours to obtain an inorganic mildew-proof antibacterial precursor;
2) transferring the inorganic mildew-proof antibacterial precursor obtained in the step 1) into a high-temperature high-pressure reaction kettle, and carrying out hydrothermal treatment at 120 DEG CCrystallizing for 72 hours, cooling, taking out, washing with water until no sulfate radical remains, and drying to obtain the nickel inorganic mildew-proof antibacterial material, wherein the chemical formula is as follows: na (Na)0.5(Si8Mg2(Ni0.3Al4)O20(OH)4)·3H2O。
Example 3:
1)1) mixing silica sol containing 0.8M of silicon dioxide, 0.27M basic magnesium carbonate, 0.03M silver nitrate, 0.03M stannous sulfate and 0.03M boric acid according to the volume ratio of 1: 1: 1:1, uniformly mixing, adjusting the pH value to 10 by using a sodium hydroxide solution, maintaining the reaction temperature at 0 ℃, and continuously stirring for 48 hours to obtain an inorganic mildew-proof antibacterial precursor;
2) transferring the inorganic mildew-proof antibacterial precursor obtained in the step 1) into a high-temperature high-pressure reaction kettle, carrying out hydrothermal crystallization at 350 ℃ for 0.1h, cooling, taking out, washing with water until no sulfate radical remains, and drying to obtain the silver inorganic mildew-proof antibacterial material, wherein the chemical formula is as follows: na (Na)0.5(Si8Mg5.4(Ag0.3Sn0.3)O20(OH)3.1(BO3)0.3)·2H2O。
Example 4:
1)1) mixing 0.8M potassium silicate, 0.34M magnesium acetate, 0.05M nickel sulfate and 0.01M titanium sulfate according to the volume ratio of 1: 1:1, uniformly mixing, adjusting the pH value to 7 by using a dilute sulfuric acid solution, maintaining the reaction temperature at 120 ℃, and continuously stirring for 0.1 hour to obtain an inorganic mildew-proof antibacterial precursor;
2) transferring the inorganic mildew-proof antibacterial precursor obtained in the step 1) into a high-temperature high-pressure reaction kettle, carrying out hydrothermal crystallization at 200 ℃ for 16h, cooling, taking out, washing with water until no sulfate radical remains, and drying to obtain the nickel inorganic mildew-proof antibacterial material, wherein the chemical formula is as follows: k0.5(Si8Mg3.4(Ni0.5Ti0.1)O20(OH)4)·7H2O。
Example 5:
1) mixing 0.8M fumed silica, 0.6M magnesium oxide +0.2M sodium fluoride, 0.05M cobalt sulfate +0.05M manganese sulfate according to a volume ratio of 1: 1:1, uniformly mixing, adjusting the pH value to 11 by using a sodium hydroxide solution, maintaining the reaction temperature at 65 ℃, and continuously stirring for 5 hours to obtain an inorganic mildew-proof antibacterial precursor;
2) transferring the inorganic mildew-proof antibacterial precursor obtained in the step 1) into a high-temperature high-pressure reaction kettle, carrying out hydrothermal crystallization at 160 ℃ for 30h, cooling, taking out, washing with water until no sulfate radical remains, and drying to obtain the cobalt inorganic mildew-proof antibacterial material, wherein the chemical formula is as follows: na (Na)0.2(Si8Mg2(Co0.5Mn0.5)O20(OH)4)·5H2O。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. An inorganic mildew-proof antibacterial material is characterized in that: can be dispersed in water or organic solvent aqueous solution to form transparent solution;
the chemical formula of the inorganic mildew-proof antibacterial material is Nak（Si8Mgx（AyBz）O20(OH)mRn）·tH2O, wherein:
a is antibacterial cation, and is selected from one or two of Co or Ag;
b is modified cation, and is selected from any one or more of Li, Na, K, Al, Ca, V, Cr, Mn, Ge and Sn;
r is selected from any one or more of C-containing anionic groups, F-containing anionic groups, As-containing anionic groups, P-containing anionic groups or B-containing anionic groups;
0≤k<1；4<x+y+z<7，0＜y+z≤5；m+n≤4；0<t<8。
2. a method for preparing the inorganic mildew-proof antibacterial material according to claim 1, which is characterized by comprising the following steps: the inorganic mildew-resistant antibacterial material of claim 1 is prepared by a hydrothermal synthesis method.
3. The method for preparing the inorganic mildew-proof antibacterial material according to claim 2, characterized by comprising the following steps:
1) mixing a magnesium-containing compound, a silicon-containing compound and a compound containing a mildew-proof antibacterial element according to a metering ratio, or mixing the magnesium-containing compound, the silicon-containing compound, the compound containing the mildew-proof antibacterial element and a modified compound according to the metering ratio, adjusting the pH value to 7-13, and reacting for 0.1-48h at the temperature of 0-120 ℃ to obtain an inorganic mildew-proof antibacterial precursor;
the magnesium-containing compound is selected from any one or more of magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium acetate, magnesium carbonate, basic magnesium carbonate, magnesium oxide and magnesium hydroxide;
the silicon-containing compound is selected from any one or mixture of more of sodium silicate, lithium silicate, potassium silicate, sodium fluosilicate, potassium fluosilicate, magnesium fluosilicate, silicon dioxide and silica sol;
the mildew-proof antibacterial element is selected from any one or mixture of silver and cobalt;
the modified compound is selected from any one or more of a lithium salt compound, a sodium salt compound, a potassium salt compound, an aluminum salt compound, a calcium salt compound, a vanadium salt compound, a chromium salt compound, a manganese salt compound, a germanium salt compound and a tin salt compound;
2) and (2) reacting the inorganic mildew-proof antibacterial precursor obtained in the step 1) at high temperature and high pressure, wherein the reaction temperature is 120-350 ℃, the reaction time is 0.1-72h, cooling after the reaction is finished, removing redundant impurities, and drying to obtain the inorganic mildew-proof antibacterial material.
4. The method for preparing the inorganic mildew-proof antibacterial material according to claim 3, characterized by comprising the following steps:
the metering ratio of the silicon-containing compound, the magnesium-containing compound, the mildew-proof antibacterial element and the modified compound is as follows: 8: 2-7: 0-1: 0-5, and the contents of the mildew-proof antibacterial element and the modified compound are not 0.
5. The use of the inorganic antifungal and antibacterial material according to claim 1, wherein: can be used as inorganic antimildew and antibacterial agent.
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| CN111436459A (en) | 2020-07-24 |
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