CN111116162B - Bactericidal and mildew-proof diatom ooze and preparation method thereof - Google Patents
Bactericidal and mildew-proof diatom ooze and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of air purification materials, and discloses bactericidal and mildew-proof diatom ooze and a preparation method thereof. The preparation method comprises the following preparation processes: (1) adding collagen, calcium phosphate and glutaraldehyde solution into hydrochloric acid for reaction to prepare calcium phosphate composite collagen fiber; (2) adding titanium dioxide, calcium phosphate composite collagen fiber and hexadecyl methyl ammonium bromide into deionized water to prepare suspension; (3) adding silver nitrate and ammonia water into the suspension, and stirring for reaction to obtain the composite bactericidal filler; (4) the composite bactericidal filler is uniformly mixed with diatomite, calcium carbonate, titanium dioxide, silica sol, vinyl acetate-ethylene copolymer rubber powder and lignocellulose to prepare the bactericidal and mildewproof diatom ooze. The composite bactericidal material in the diatom ooze prepared by the invention has good biocompatibility, can induce bacteria to adhere to the surface, and simultaneously, the silver bromide can enhance the photocatalytic performance of titanium dioxide, thereby realizing good bactericidal and mildew-proof performances.
Description
Technical Field
The invention relates to the technical field of air purification materials, and discloses bactericidal and mildew-proof diatom ooze and a preparation method thereof.
Background
Diatomite is a siliceous rock and has the properties of fineness, looseness, light weight, porosity, water absorption and strong permeability, so the diatomite is often used as a building material and has the advantages of no toxicity, environmental protection and the like. Diatomite has many natural advantages and is beneficial to improving indoor environment. The diatom ooze is a pure natural mineral material, so that the diatom ooze is neither smelly nor toxic, and can eliminate formaldehyde in air and purify indoor air where people live.
The diatom ooze has very excellent adsorption performance, and therefore, has good adsorption performance for moisture and bacteria. Traditional diatomaceous earth does not have the function of disinfecting, therefore the diatomaceous earth micropore provides good living space for the bacterium breeds fast, thereby causes the wall body to go mildy and rot, influences indoor air quality, harms people's health. Therefore, the diatom ooze is endowed with sterilization performance and is particularly important for maintaining indoor air quality.
At present, the technical method for endowing diatom ooze with sterilization performance generally utilizes diatom ooze to load functional fillers with sterilization performance such as nano silver and the like. The nano silver particles directly enter the thallus to be combined with oxygen metabolic enzyme, so that the thallus is choked to death by a unique action mechanism, most of bacteria, fungi, mould, spores and other microorganisms which are contacted with the thallus can be killed, and therefore, the bactericidal performance of the diatom ooze can be realized by adding the nano silver into the diatom ooze.
The Chinese patent application number 201610205534.7 discloses a silver-loaded nano titanium dioxide mildew-proof diatom ooze and a preparation method thereof, and specifically comprises the following steps: firstly, 10-30 wt% of silver-loaded nano titanium dioxide is prepared into pre-pulping, and then the pre-pulping is mixed with 20-35 wt% of deionized water, 0.8-3 wt% of an antifreezing agent, 2-5 wt% of a nano silicon dioxide solution, 0.2-1.0 wt% of a thickening agent, 0.5-3 wt% of bentonite, 3-15 wt% of titanium dioxide, 5-20 wt% of gray calcium, 25-40 wt% of diatomite, 0.1-0.8 wt% of a retarder and 0.1-2 wt% of a gray calcium stabilizer to prepare diatom ooze.
Chinese patent application No. 201510570099.3 discloses an environment-friendly bactericidal diatom ooze coating which comprises the following raw materials in parts by weight: 50-55 parts of natural diatomite, 15-20 parts of anion powder, 10-13 parts of sepiolite powder, 7-10 parts of polylactic acid chelated silver ion bactericide, 7-9 parts of vermiculite powder, 3.2-3.6 parts of flexibilizer, 1.2-1.5 parts of emulsifier, 1.2-1.5 parts of curing agent, 1.4-1.7 parts of defoaming agent, 1.3-1.6 parts of advection agent, 0.7-1 part of advection auxiliary agent, 0.8-1.2 parts of mildew preventive, 1.8-2.2 parts of dispersing agent, 1.2-1.5 parts of film-forming auxiliary agent and 55-60 parts of deionized water.
According to the above, in the prior art, the technical method for realizing the sterilization and mildew-proof performance of the diatom ooze is usually to add antibacterial fillers such as nano silver into the diatom ooze or directly load silver-loaded nano titanium dioxide on the diatom ooze, but both methods have low sterilization efficiency due to less contact between silver and bacteria.
Disclosure of Invention
At present, widely applied diatom ooze with sterilization and mildew prevention performances is generally realized by adding nano silver and other sterilization materials, so that the problem of low sterilization efficiency generally exists, and the application of the diatom ooze with sterilization and mildew prevention is restricted.
The invention achieves the above purpose by the following technical scheme:
a preparation method of bactericidal and mildewproof diatom ooze comprises the following specific steps:
(1) firstly, putting collagen into hydrochloric acid with the mass concentration of 37% to be soaked for 120h, uniformly stirring to obtain milk white suspension, then adding calcium phosphate to be uniformly stirred, then adding glutaraldehyde solution with the mass concentration of 0.2%, stirring for 1h, and further performing freeze drying to obtain calcium phosphate composite collagen fibers;
(2) firstly, adding titanium dioxide into deionized water, stirring and dispersing uniformly, then adding the calcium phosphate composite collagen fiber obtained in the step (1) and hexadecyl methyl ammonium bromide, and strongly stirring to obtain a suspension;
(3) adding silver nitrate and ammonia water into the suspension prepared in the step (2), stirring at room temperature for 18-20 h, filtering and washing the product, drying at 80-110 ℃ for 2-4 h, and irradiating under ultraviolet light for 3-4 h to prepare the silver/silver bromide-loaded nano titanium dioxide coated by the calcium phosphate composite collagen fibers;
(4) and (4) uniformly mixing the silver/silver bromide-loaded nano titanium dioxide coated with the calcium phosphate composite collagen fiber obtained in the step (3), diatomite, calcium carbonate, titanium dioxide, silica sol, vinyl acetate-ethylene copolymer rubber powder and lignocellulose to obtain the bactericidal and mildewproof diatom ooze.
The invention firstly utilizes the collagen to prepare the collagen fiber which is a viscoelastic body, has obvious hysteresis and stress relaxation characteristics, can cause very high stress by very small strain, has very strong rigidity and has adsorption performance, and especially has very good adsorption effect on organic matters. The collagen fiber is further compounded with calcium phosphate, the calcium phosphate has good biocompatibility and bioactivity, and the obtained calcium phosphate composite collagen fiber can form a good coating layer on the surface of the inorganic filler. Preferably, the collagen in the step (1) is commercially available collagen powder; the temperature of the freeze drying is-50 to-10 ℃, and the time is 5 to 10 hours; the raw materials comprise, by weight, 5-10 parts of collagen, 5-15 parts of calcium phosphate, 15-30 parts of hydrochloric acid and 1-5 parts of glutaraldehyde solution.
Titanium dioxide exists in nature in three crystal structures: rutile type, anatase type and brookite type, wherein rutile type and anatase type titanium dioxide have high catalytic activity and good antibacterial performance. Preferably, the titanium dioxide in the step (2) is titanium dioxide of anatase crystal and rutile crystal mixed phase with the average particle size of 25 nm.
Preferably, the stirring speed of the intensive stirring in the step (2) is 500-1000 r/min, and the time is 10-30 min.
The invention adds titanium dioxide, calcium phosphate composite collagen fiber and hexadecyl methyl ammonium bromide into water to prepare suspension, further reacts with silver nitrate and ammonia water, silver and silver bromide can be obtained by reaction and loaded on the surface of titanium dioxide, and the calcium phosphate composite collagen fiber is coated at the same time to obtain the nano titanium dioxide coated with silver/silver bromide and coated by the calcium phosphate composite collagen fiber. The calcium phosphate composite collagen fiber has excellent biocompatibility, the organic collagen nanofiber can induce bacteria to adhere to the surface of the calcium phosphate composite collagen fiber, so that the sterilization efficiency of the sterilization material is improved, meanwhile, the silver bromide serving as the photosensitive material can enhance the visible light photocatalysis capability of the titanium dioxide, the sterilization efficiency of the titanium dioxide is improved under visible light, and the diatom ooze material prepared by the silver bromide serving as the functional filler has an excellent sterilization and mildew-proof effect. Preferably, the raw materials in the step (2) are 10 to 30 parts by weight of titanium dioxide, 15 to 40 parts by weight of deionized water, 5 to 15 parts by weight of calcium phosphate composite collagen fiber, and 1 to 3 parts by weight of hexadecyl methyl ammonium bromide.
Preferably, the raw materials in the step (3) are 50-80 parts by weight of the suspension, 20-30 parts by weight of silver nitrate and 5-10 parts by weight of ammonia water.
Preferably, the raw materials in the step (4) are 5-10 parts by weight of silver-loaded/silver bromide nano titanium dioxide coated with calcium phosphate composite collagen fibers, 35-50 parts by weight of diatomite, 5-10 parts by weight of calcium carbonate, 3-5 parts by weight of titanium dioxide, 5-15 parts by weight of silica sol, 1-3 parts by weight of vinyl acetate-ethylene copolymer rubber powder and 1-5 parts by weight of lignocellulose.
The bactericidal and mildewproof diatom ooze prepared by the method has good bactericidal performance. Through tests, the antibacterial rate of escherichia coli of the prepared diatom ooze is 99.12-99.45%, the antibacterial rate of staphylococcus aureus is 98.77-99.09%, and the antibacterial rate of white-shaped coccobacillus is more than 99.99%.
The invention provides a bactericidal and mildew-proof diatom ooze and a preparation method thereof.A collagen is put into hydrochloric acid to be soaked for 120 hours and then stirred to obtain a milky suspension, calcium phosphate is added and stirred, a glutaraldehyde solution is continuously added, and after stirring, freeze drying is carried out to obtain calcium phosphate composite collagen fibers; adding titanium dioxide into water, stirring and dispersing, adding calcium phosphate composite collagen fibers and hexadecyl methyl ammonium bromide, and strongly stirring to obtain a suspension; continuously adding silver nitrate and ammonia water into the suspension, stirring at room temperature, filtering, washing and drying the obtained product, and irradiating the product under ultraviolet light to obtain the nano titanium dioxide coated with the silver/silver bromide and coated by the calcium phosphate composite collagen fiber; and uniformly mixing the obtained calcium phosphate composite collagen fiber coated silver-loaded/silver bromide nano titanium dioxide, diatomite, calcium carbonate, titanium dioxide, silica sol, vinyl acetate-ethylene copolymer rubber powder and lignocellulose.
The invention provides a bactericidal and mildew-proof diatom ooze and a preparation method thereof, compared with the prior art, the bactericidal and mildew-proof diatom ooze has the outstanding characteristics and excellent effects that:
1. provides a method for preparing bactericidal and mildewproof diatom ooze by coating silver/silver bromide-loaded nano titanium dioxide with calcium phosphate composite collagen fibers.
2. The nano titanium dioxide carrying silver/silver bromide is coated by the calcium phosphate composite collagen fiber, so that the prepared sterilization material has biocompatibility, and the organic collagen fiber can better induce bacteria to adhere to the surface of the collagen fiber, thereby realizing better contact between the sterilization material and the bacteria and achieving better sterilization effect.
3. The silver bromide in the prepared bactericidal material is used as a photosensitive material, so that the visible light photocatalysis capacity of titanium dioxide can be effectively enhanced, and the bactericidal and mildewproof effects of the diatom ooze material are further improved.
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FIG. 1 is a schematic view of a preparation process of the bactericidal and mildewproof diatom ooze.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Firstly, putting collagen into hydrochloric acid with the mass concentration of 37% to be soaked for 120h, uniformly stirring to obtain milk white suspension, then adding calcium phosphate to be uniformly stirred, then adding glutaraldehyde solution with the mass concentration of 0.2%, stirring for 1h, and further performing freeze drying to obtain calcium phosphate composite collagen fibers; the temperature of freeze drying is-10 ℃ and the time is 5 h;
the raw materials comprise, by weight, 10 parts of collagen, 15 parts of calcium phosphate, 15 parts of hydrochloric acid and 3 parts of glutaraldehyde solution;
(2) firstly, adding titanium dioxide into deionized water, stirring and dispersing uniformly, then adding the calcium phosphate composite collagen fiber obtained in the step (1) and hexadecyl methyl ammonium bromide, and strongly stirring to obtain a suspension; the titanium dioxide is titanium dioxide of anatase crystal and rutile crystal mixed phase with the average grain diameter of 25 nm; the stirring speed of the intensive stirring is 1000r/min, and the time is 10 min;
the raw materials comprise, by weight, 30 parts of titanium dioxide, 15 parts of deionized water, 5 parts of calcium phosphate composite collagen fiber and 3 parts of hexadecyl methyl ammonium bromide;
(3) adding silver nitrate and ammonia water into the suspension prepared in the step (2), stirring at room temperature for 20h, filtering and washing the product, drying at 110 ℃ for 2h, and irradiating under ultraviolet light for 4h to prepare the silver/silver bromide-loaded nano titanium dioxide coated by the calcium phosphate composite collagen fiber;
the raw materials comprise, by weight, 50 parts of suspension, 20 parts of silver nitrate and 10 parts of ammonia water;
(4) uniformly mixing the silver/silver bromide-loaded nano titanium dioxide coated with the calcium phosphate composite collagen fibers obtained in the step (3), diatomite, calcium carbonate, titanium dioxide, silica sol, vinyl acetate-ethylene copolymer rubber powder and lignocellulose to obtain the bactericidal and mildewproof diatom ooze;
the raw materials comprise, by weight, 10 parts of silver-loaded/silver bromide nano titanium dioxide coated by calcium phosphate composite collagen fibers, 50 parts of diatomite, 5 parts of calcium carbonate, 3 parts of titanium dioxide, 5 parts of silica sol, 3 parts of vinyl acetate-ethylene copolymer rubber powder and 5 parts of lignocellulose.
Example 2
(1) Firstly, putting collagen into hydrochloric acid with the mass concentration of 37% to be soaked for 120h, uniformly stirring to obtain milk white suspension, then adding calcium phosphate to be uniformly stirred, then adding glutaraldehyde solution with the mass concentration of 0.2%, stirring for 1h, and further performing freeze drying to obtain calcium phosphate composite collagen fibers; the temperature of freeze drying is-50 ℃ and the time is 10 h;
the raw materials comprise, by weight, 5 parts of collagen, 15 parts of calcium phosphate, 20 parts of hydrochloric acid and 4 parts of glutaraldehyde solution;
(2) firstly, adding titanium dioxide into deionized water, stirring and dispersing uniformly, then adding the calcium phosphate composite collagen fiber obtained in the step (1) and hexadecyl methyl ammonium bromide, and strongly stirring to obtain a suspension; the titanium dioxide is titanium dioxide of anatase crystal and rutile crystal mixed phase with the average grain diameter of 25 nm; the stirring speed of the intensive stirring is 500r/min, and the time is 30 min;
the raw materials comprise, by weight, 10 parts of titanium dioxide, 40 parts of deionized water, 5 parts of calcium phosphate composite collagen fiber and 3 parts of hexadecyl methyl ammonium bromide;
(3) adding silver nitrate and ammonia water into the suspension prepared in the step (2), stirring at room temperature for 18h, filtering and washing the product, drying at 80 ℃ for 4h, and irradiating under ultraviolet light for 3h to prepare the silver/silver bromide-loaded nano titanium dioxide coated by the calcium phosphate composite collagen fiber;
the mixture ratio of the raw materials is, by weight, 70 parts of suspension, 28 parts of silver nitrate and 8 parts of ammonia water;
(4) uniformly mixing the silver/silver bromide-loaded nano titanium dioxide coated with the calcium phosphate composite collagen fibers obtained in the step (3), diatomite, calcium carbonate, titanium dioxide, silica sol, vinyl acetate-ethylene copolymer rubber powder and lignocellulose to obtain the bactericidal and mildewproof diatom ooze;
the raw materials comprise, by weight, 7 parts of silver-loaded/silver bromide nano titanium dioxide coated by calcium phosphate composite collagen fibers, 48 parts of diatomite, 8 parts of calcium carbonate, 3 parts of titanium dioxide, 12 parts of silica sol, 2 parts of vinyl acetate-ethylene copolymer rubber powder and 2 parts of lignocellulose.
Example 3
(1) Firstly, putting collagen into hydrochloric acid with the mass concentration of 37% to be soaked for 120h, uniformly stirring to obtain milk white suspension, then adding calcium phosphate to be uniformly stirred, then adding glutaraldehyde solution with the mass concentration of 0.2%, stirring for 1h, and further performing freeze drying to obtain calcium phosphate composite collagen fibers; the temperature of freeze drying is-20 ℃, and the time is 7 h;
the raw materials comprise, by weight, 5 parts of collagen, 5 parts of calcium phosphate, 30 parts of hydrochloric acid and 3 parts of glutaraldehyde solution;
(2) firstly, adding titanium dioxide into deionized water, stirring and dispersing uniformly, then adding the calcium phosphate composite collagen fiber obtained in the step (1) and hexadecyl methyl ammonium bromide, and strongly stirring to obtain a suspension; the titanium dioxide is titanium dioxide of anatase crystal and rutile crystal mixed phase with the average grain diameter of 25 nm; the stirring speed of the intensive stirring is 800r/min, and the time is 20 min;
the raw materials comprise, by weight, 30 parts of titanium dioxide, 15 parts of deionized water, 15 parts of calcium phosphate composite collagen fiber and 3 parts of hexadecyl methyl ammonium bromide;
(3) adding silver nitrate and ammonia water into the suspension prepared in the step (2), stirring at room temperature for 18h, filtering and washing the product, drying at 100 ℃ for 3h, and irradiating under ultraviolet light for 4h to prepare the silver/silver bromide-loaded nano titanium dioxide coated by the calcium phosphate composite collagen fiber;
the raw materials comprise, by weight, 50 parts of suspension, 20 parts of silver nitrate and 10 parts of ammonia water;
(4) uniformly mixing the silver/silver bromide-loaded nano titanium dioxide coated with the calcium phosphate composite collagen fibers obtained in the step (3), diatomite, calcium carbonate, titanium dioxide, silica sol, vinyl acetate-ethylene copolymer rubber powder and lignocellulose to obtain the bactericidal and mildewproof diatom ooze;
the raw materials comprise, by weight, 10 parts of silver-loaded/silver bromide nano titanium dioxide coated by calcium phosphate composite collagen fibers, 50 parts of diatomite, 10 parts of calcium carbonate, 5 parts of titanium dioxide, 15 parts of silica sol, 2 parts of vinyl acetate-ethylene copolymer rubber powder and 5 parts of lignocellulose.
Example 4
(1) Firstly, putting collagen into hydrochloric acid with the mass concentration of 37% to be soaked for 120h, uniformly stirring to obtain milk white suspension, then adding calcium phosphate to be uniformly stirred, then adding glutaraldehyde solution with the mass concentration of 0.2%, stirring for 1h, and further performing freeze drying to obtain calcium phosphate composite collagen fibers; the temperature of freeze drying is-40 ℃, and the time is 6 h;
the raw materials comprise, by weight, 5 parts of collagen, 5 parts of calcium phosphate, 30 parts of hydrochloric acid and 1 part of glutaraldehyde solution;
(2) firstly, adding titanium dioxide into deionized water, stirring and dispersing uniformly, then adding the calcium phosphate composite collagen fiber obtained in the step (1) and hexadecyl methyl ammonium bromide, and strongly stirring to obtain a suspension; the titanium dioxide is titanium dioxide of anatase crystal and rutile crystal mixed phase with the average grain diameter of 25 nm; the stirring speed of the intensive stirring is 600r/min, and the time is 25 min;
the raw materials comprise, by weight, 30 parts of titanium dioxide, 40 parts of deionized water, 15 parts of calcium phosphate composite collagen fiber and 1 part of hexadecyl methyl ammonium bromide;
(3) adding silver nitrate and ammonia water into the suspension prepared in the step (2), stirring at room temperature for 20h, filtering and washing the product, drying at 110 ℃ for 2h, and irradiating under ultraviolet light for 4h to prepare the silver/silver bromide-loaded nano titanium dioxide coated by the calcium phosphate composite collagen fiber;
the raw materials comprise 68 parts by weight of suspension, 22 parts by weight of silver nitrate and 8 parts by weight of ammonia water;
(4) uniformly mixing the silver/silver bromide-loaded nano titanium dioxide coated with the calcium phosphate composite collagen fibers obtained in the step (3), diatomite, calcium carbonate, titanium dioxide, silica sol, vinyl acetate-ethylene copolymer rubber powder and lignocellulose to obtain the bactericidal and mildewproof diatom ooze;
the raw materials comprise, by weight, 8 parts of silver-loaded/silver bromide nano titanium dioxide coated by calcium phosphate composite collagen fibers, 38 parts of diatomite, 5 parts of calcium carbonate, 3 parts of titanium dioxide, 13 parts of silica sol, 3 parts of vinyl acetate-ethylene copolymer rubber powder and 3 parts of lignocellulose.
Example 5
(1) Firstly, putting collagen into hydrochloric acid with the mass concentration of 37% to be soaked for 120h, uniformly stirring to obtain milk white suspension, then adding calcium phosphate to be uniformly stirred, then adding glutaraldehyde solution with the mass concentration of 0.2%, stirring for 1h, and further performing freeze drying to obtain calcium phosphate composite collagen fibers; the temperature of freeze drying is-10 ℃ and the time is 8 h;
the raw materials comprise, by weight, 6 parts of collagen, 9 parts of calcium phosphate, 25 parts of hydrochloric acid and 2 parts of glutaraldehyde solution;
(2) firstly, adding titanium dioxide into deionized water, stirring and dispersing uniformly, then adding the calcium phosphate composite collagen fiber obtained in the step (1) and hexadecyl methyl ammonium bromide, and strongly stirring to obtain a suspension; the titanium dioxide is titanium dioxide of anatase crystal and rutile crystal mixed phase with the average grain diameter of 25 nm; the stirring speed of the intensive stirring is 600r/min, and the time is 15 min;
the raw materials comprise, by weight, 15 parts of titanium dioxide, 30 parts of deionized water, 6 parts of calcium phosphate composite collagen fiber and 2 parts of hexadecyl methyl ammonium bromide;
(3) adding silver nitrate and ammonia water into the suspension prepared in the step (2), stirring at room temperature for 20h, filtering and washing the product, drying at 80 ℃ for 4h, and irradiating under ultraviolet light for 4h to prepare the silver/silver bromide-loaded nano titanium dioxide coated by the calcium phosphate composite collagen fiber;
the raw materials comprise 65 parts by weight of suspension, 28 parts by weight of silver nitrate and 6 parts by weight of ammonia water;
(4) uniformly mixing the silver/silver bromide-loaded nano titanium dioxide coated with the calcium phosphate composite collagen fibers obtained in the step (3), diatomite, calcium carbonate, titanium dioxide, silica sol, vinyl acetate-ethylene copolymer rubber powder and lignocellulose to obtain the bactericidal and mildewproof diatom ooze;
the raw materials comprise, by weight, 8 parts of silver-loaded/silver bromide nano titanium dioxide coated by calcium phosphate composite collagen fibers, 44 parts of diatomite, 7 parts of calcium carbonate, 4 parts of titanium dioxide, 10 parts of silica sol, 3 parts of vinyl acetate-ethylene copolymer rubber powder and 2 parts of lignocellulose.
Comparative example 1
Comparative example 1 in which the calcium phosphate composite collagen fiber was not added and the preparation conditions were the same as in example 1, the antibacterial rates against escherichia coli, staphylococcus aureus, and leucococcus albidus of the obtained bactericidal and mildewproof diatom ooze are shown in table 1.
The test was performed with reference to HG/T3950-2007, in which the samples prepared in example and comparative example 1 were spread on an agar medium, a spore suspension containing escherichia coli, staphylococcus aureus, and candida albicans was sprayed sufficiently uniformly on the medium and the sample, and then the sample was incubated at a temperature of 28 ℃ and a relative temperature of 90% for 28 days, and the number of bacteria was measured by a microbial limit detector.
As can be seen from table 1: the antibacterial rate of the embodiment to escherichia coli and staphylococcus aureus is higher than that of the comparative example 1, and the following results are shown: the calcium phosphate composite collagen fiber is coated with the silver/silver bromide nano titanium dioxide, so that the sterilization material has biocompatibility, and can better induce bacteria to adhere to the surface of the sterilization material, thereby realizing better sterilization effect.
Table 1:
Claims (9)
1. the preparation method of the bactericidal and mildewproof diatom ooze is characterized by comprising the following specific steps:
(1) firstly, putting collagen into hydrochloric acid with the mass concentration of 37% to be soaked for 120h, uniformly stirring to obtain milk white suspension, then adding calcium phosphate to be uniformly stirred, then adding glutaraldehyde solution with the mass concentration of 0.2%, stirring for 1h, and further performing freeze drying to obtain calcium phosphate composite collagen fibers;
(2) firstly, adding titanium dioxide into deionized water, stirring and dispersing uniformly, then adding the calcium phosphate composite collagen fiber obtained in the step (1) and hexadecyl methyl ammonium bromide, and strongly stirring to obtain a suspension; the titanium dioxide is titanium dioxide of an anatase crystal and rutile crystal mixed phase with the average particle size of 25 nm;
(3) adding silver nitrate and ammonia water into the suspension prepared in the step (2), stirring at room temperature for 18-20 h, filtering and washing the product, drying at 80-110 ℃ for 2-4 h, and irradiating under ultraviolet light for 3-4 h to prepare the silver/silver bromide-loaded nano titanium dioxide coated by the calcium phosphate composite collagen fibers;
(4) and (4) uniformly mixing the silver/silver bromide-loaded nano titanium dioxide coated with the calcium phosphate composite collagen fiber obtained in the step (3), diatomite, calcium carbonate, titanium dioxide, silica sol, vinyl acetate-ethylene copolymer rubber powder and lignocellulose to obtain the bactericidal and mildewproof diatom ooze.
2. The method for preparing the bactericidal and mildewproof diatom ooze according to claim 1, wherein the method comprises the following steps: the collagen in the step (1) is commercial collagen powder.
3. The method for preparing the bactericidal and mildewproof diatom ooze according to claim 1, wherein the method comprises the following steps: the temperature of the freeze drying in the step (1) is-50 to-10 ℃, and the time is 5 to 10 hours.
4. The method for preparing the bactericidal and mildewproof diatom ooze according to claim 1, wherein the method comprises the following steps: the raw materials in the step (1) are 5-10 parts by weight of collagen, 5-15 parts by weight of calcium phosphate, 15-30 parts by weight of hydrochloric acid and 1-5 parts by weight of glutaraldehyde solution.
5. The method for preparing the bactericidal and mildewproof diatom ooze according to claim 1, wherein the method comprises the following steps: the stirring speed of the intensive stirring in the step (2) is 500-1000 r/min, and the time is 10-30 min.
6. The method for preparing the bactericidal and mildewproof diatom ooze according to claim 1, wherein the method comprises the following steps: the raw materials in the step (2) comprise, by weight, 10-30 parts of titanium dioxide, 15-40 parts of deionized water, 5-15 parts of calcium phosphate composite collagen fibers and 1-3 parts of hexadecyl methyl ammonium bromide.
7. The method for preparing the bactericidal and mildewproof diatom ooze according to claim 1, wherein the method comprises the following steps: the raw materials in the step (3) are 50-80 parts by weight of the suspension, 20-30 parts by weight of silver nitrate and 5-10 parts by weight of ammonia water.
8. The method for preparing the bactericidal and mildewproof diatom ooze according to claim 1, wherein the method comprises the following steps: the raw materials in the step (4) are 5-10 parts by weight of silver-loaded/silver bromide nano titanium dioxide coated by calcium phosphate composite collagen fibers, 35-50 parts by weight of diatomite, 5-10 parts by weight of calcium carbonate, 3-5 parts by weight of titanium dioxide, 5-15 parts by weight of silica sol, 1-3 parts by weight of vinyl acetate-ethylene copolymer rubber powder and 1-5 parts by weight of lignocellulose.
9. A bactericidal and mould proof diatom ooze prepared by the method of any one of claims 1-8.
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