CN115399333A - Preparation method and application of antibacterial nano composite material - Google Patents
Preparation method and application of antibacterial nano composite material Download PDFInfo
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- CN115399333A CN115399333A CN202211141827.5A CN202211141827A CN115399333A CN 115399333 A CN115399333 A CN 115399333A CN 202211141827 A CN202211141827 A CN 202211141827A CN 115399333 A CN115399333 A CN 115399333A
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
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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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
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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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a preparation method and application of an antibacterial nano composite material. The antibacterial nano composite material which is transparent in color, durable and stable in antibacterial effect and uniform in size is prepared by a simple preparation method, the antibacterial rate of the material to escherichia coli is more than 99%, the antibacterial rate to staphylococcus aureus is more than 99%, the antibacterial rate to candida albicans is more than 90%, the antibacterial nano composite material is suitable for the technical field of functional nano materials, and can be used as an antibacterial material for coatings, textiles, protective articles, medical materials, plastic vessels, digital products and household electrical appliance products.
Description
Technical Field
The invention belongs to the technical field of functional nano materials, and relates to an antibacterial nano material, in particular to a preparation method and application of an antibacterial nano composite material.
Background
Along with the improvement of modern life quality, the attention degree of people to health and safety is gradually improved, and concepts such as health protection, ecological environment protection and the like are widely concerned in the consumer market. Because bacteria are closely related to the production and life of human beings, the antibacterial and bacteriostatic effects are the problems facing all industries, and along with the change of consumption concepts of people, the antibacterial performance of materials in kitchen and bathroom appliances is gradually concerned; in addition, antibacterial materials for protection, bandaging, correction and other purposes are hot spots for developing medical materials.
Currently, the antibacterial material can be divided into a single-component antibacterial material and a composite antibacterial material according to the difference of the types of antibacterial substances. However, the single-component antibacterial material has poor antibacterial property, is often used in a large amount to improve the antibacterial effect, has the problems of dark color, poor heat resistance, difficult dispersion and the like, and is difficult to meet the requirements of various industries.
In recent years, the research on composite antibacterial materials has been receiving much attention, but certain problems still remain. In the Chinese patent application with publication number CN113801457A, polyhexamethylene guanidine hydrochloride (PHMG) is modified by epichlorohydrin, tannic acid is added as a complexing agent, and the tannic acid and ferroferric oxide are subjected to a complexing reaction to generate a composite antibacterial material, but the nano size of the material generated by the method is uncontrollable, the retention rate of the PHMG in the ferroferric oxide after washing is reduced, the antibacterial effect is influenced, and the composite antibacterial agent has a color; the Chinese patent application with publication number CN112853747A is that silver nitrate and sodium borohydride are added into a PHMG aqueous solution system, and a nano silver-PHMG composite treating agent is generated through reduction reaction, because nano silver is not easy to disperse in the PHMG solution, the compatibility among matrixes is not high, and the pollution to the environment is easy to generate; in the Chinese patent application with publication No. CN110354304A, because PHMG is only coated on the surface of titanium dioxide, the antibacterial time of the obtained material is limited; in the application of the Chinese patent with the publication number CN112998884B, when the porous nano tourmaline is modified, the method of grafting the antibacterial agent is adopted, grafting reaction is carried out for more than 8 hours in a constant temperature environment of 150-180 ℃, and the problems of high energy consumption, long reaction time and the like exist.
Disclosure of Invention
The invention aims to provide a preparation method of an antibacterial nano composite material, which achieves the aim of preparing the antibacterial nano composite material with transparent color, lasting and stable antibacterial effect and uniform size by a simple preparation method through the synergistic effect of porous tourmaline, organic macromolecular antibacterial agent containing guanidyl, benzotriazole and metal salt.
The invention also aims to provide the application of the preparation method in preparing the antibacterial fiber material with the organic polymer material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a process for preparing antibacterial nano-class composition includes loading guanidyl-containing organic high-molecular antibacterial agent onto porous tourmaline as carrier to obtain functional hybridized material, pulverizing, and sealing the surface of said functional hybridized material with benzotriazole and metallic salt solution.
As a limitation of the present invention, the preparation method comprises the following steps performed in sequence:
s1, taking porous tourmaline and organic polymer antibacterial agent solution containing guanidyl, performing ultrasonic treatment, and placing in a vacuum environment to obtain a functional hybrid material;
s2, grinding the functional hybrid material and benzotriazole into powder, adding water, mixing uniformly, carrying out vacuum filtration at 80-90 ℃, and drying to obtain a composite functional hybrid material;
and S3, adding the composite functional hybrid material into a metal salt solution, standing for 1-2h, washing, carrying out vacuum filtration, drying and carrying out ultraviolet irradiation to obtain the antibacterial nano composite material.
The benzotriazole is easily dissolved in water, a water system is adopted in S2, so that the benzotriazole and the functional hybrid material are fully mixed, and the benzotriazole is greatly reserved in gaps of the functional hybrid material, so that the stable structure of a protective sealing film formed subsequently is facilitated.
As a further limitation of the invention, the porous tourmaline is obtained by acidifying tourmaline, washing, vacuum filtering and drying;
the display value of the pressure gauge in the vacuum environment is-0.1 to-0.02 MPa, and the time for placing the pressure gauge in the vacuum environment is 1 to 3 hours;
the display value of a pressure gauge during vacuum filtration is-0.1 to-0.02 MPa, and the filtration time is 1 to 5min;
the solvents of the guanidino-containing organic polymer antibacterial agent solution and the metal salt solution are water;
the water flow speed of the washing is 50-100m/s;
the ultraviolet wavelength of the ultraviolet irradiation is 185-254nm, and the irradiation time is 10-30min. As a further limitation of the invention, the acidification is to treat the tourmaline with sulfuric acid to 60-80% of the mass before treatment.
As a further limitation of the invention, the mass ratio of the porous tourmaline, the guanidyl-containing organic polymer antibacterial agent and the metal salt is 1-10:1:1-10.
As a still further limitation of the present invention, the molar ratio of metal salt to benzotriazole is 1:1-3.
In another embodiment of the present invention, the organic polymeric antimicrobial agent containing a guanidino group is at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, and polyhexamethylene guanidine phosphate.
As a further limitation of the invention, the metal salt is at least one of copper chloride, copper sulfate, silver nitrate, zinc sulfate, magnesium sulfate and zinc chloride.
As a further limitation of the present invention, the antibacterial nanocomposite has a particle diameter of 300 to 700nm.
The invention provides an application of the preparation method, and the antibacterial nano composite material is prepared according to the preparation method and then used as an antibacterial material for coatings, textiles, protective articles, medical materials, plastic vessels, digital products and household electrical appliances.
Wherein, the antibacterial nano composite material and the organic polymer material are used for preparing antibacterial fiber, and then the textile is obtained through melt spinning and spinning; the antibacterial fiber is used for preparing medical materials such as masks, gauzes, dental appliances, medicine external packages and the like; in addition, the antibacterial nano composite material is also used for being added into shells and screen materials of digital products such as mobile phones and the like, so that the antibacterial performance of the digital products is improved; the antibacterial nano composite material is also used for being added into plastic or alloy materials so as to improve the antibacterial performance of household appliances such as water purifiers, washing machines, refrigerators and the like.
The principle of the invention is as follows: the inner cavity of the tourmaline is etched through sulfuric acid acidification to form the porous tourmaline, the porous tourmaline adsorbs an organic high-molecular antibacterial agent containing guanidyl by utilizing cation exchange and capillary effect in a vacuum environment, a stable film-shaped structure is formed on the surface by utilizing benzotriazole and metal salt and is attached to the surface of a material to form a protective sealing film, all components are definite in work division, and a stable multi-component antibacterial system is formed through synergistic construction to amplify the antibacterial effect.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
(1) According to the preparation method provided by the invention, porous tourmaline is used as a carrier, after the guanidyl-containing organic polymer antibacterial agent is adsorbed by the porous tourmaline, the loading capacity of benzotriazole is improved by drying at 80-90 ℃, the loading capacity of metal ions in the composite material is increased by using benzotriazole and free metal ions, and a protective sealing film can be formed on the surface of a functional hybrid material, so that the internal antibacterial component is prevented from being directly exposed in air or solution, the water washing resistance and the oxidation resistance of the material are improved, and the water washing resistance and the oxidation resistance are improved; in the preparation of the porous tourmaline, the loading capacity of the antibacterial agent is regulated and controlled by controlling the quality of the acidified tourmaline; the surface electron arrangement of the tourmaline is changed by high-speed flushing at the water flow speed of 50-100m/s, so that the tourmaline is positively charged, and is beneficial to attracting negatively charged bacteria, thereby improving the antibacterial effect; the antibacterial nano composite material is irradiated by ultraviolet light, so that BTA on the surface of the material is slowly decomposed, and the contact part of metal elements and air is slowly oxidized to generate metal oxide, so that the antibacterial effect of the material is improved;
(2) The raw materials used in the preparation method are transparent in color, and the antibacterial nano composite material prepared by grinding for multiple times is transparent and has the size of 300-700nm, so that compared with an antibacterial material with deep color and larger particle size, the application scenes in the fields of medical use, household appliances and the like are widened;
(3) The antibacterial nano composite material prepared by the invention has an excellent antibacterial effect, and has an antibacterial rate of more than 99% for escherichia coli, an antibacterial rate of more than 99% for staphylococcus aureus and an antibacterial rate of more than 90% for candida albicans;
(4) The invention is also suitable for preparing the antibacterial fiber material, the powdery antibacterial nano composite material is prepared, then the powdery antibacterial nano composite material is mixed with the organic polymer material for granulation, and the antibacterial fiber material is prepared by a melting method.
The invention is described in further detail below with reference to the figures and the embodiments.
Drawings
Fig. 1 is a scanning electron microscope and a transmission electron microscope photograph of an antibacterial nanocomposite C1 prepared in example 1 of the present invention, fig. 1 (a) and 1 (b) are scanning electron microscopes, and fig. 1 (C) and 1 (d) are transmission electron microscopes;
FIG. 2 is a photograph showing the result of measuring the antibacterial effect of the antibacterial nanocomposite C1 according to example 1 of the present invention;
FIG. 3 is a graph showing the comparison of antibacterial effects in example 8 of the present invention;
FIG. 4 is a graph showing the results of the long-acting antibacterial effect test of the antibacterial nanocomposite obtained in example 9 of the present invention.
Detailed Description
Example 1 preparation of an antibacterial nanocomposite
The preparation method of the embodiment is that porous tourmaline is used as a carrier, after an organic macromolecular antimicrobial agent containing guanidyl is loaded, a functional hybrid material is obtained, and the functional hybrid material is prepared by crushing and then sealing the surface of the functional hybrid material by benzotriazole and a metal salt solution.
Preparation method of (I) antibacterial nano composite material C1
S0: preparing porous tourmaline: taking 30g of ferroelectric tourmaline particles and concentrated sulfuric acid to immerse the ferroelectric tourmaline, heating and activating at 60 ℃, taking out after the ferroelectric tourmaline is acidified and etched to 18.2g (60.7% before treatment), centrifugally cleaning with water until the supernatant and the ferroelectric tourmaline are neutral, vacuum drying, and grinding into powder to obtain the porous tourmaline for later use.
S1: dissolving 2.2g polyhexamethylene guanidine hydrochloride (PHMG) in 80mL water, adding the obtained porous tourmaline, performing ultrasonic treatment for 30min, and placing in a vacuum chamber with a pressure gauge of-0.1 MPa for 1h; and repeating the ultrasonic treatment for 3 times, washing the surface with water, drying in an oven at 60 ℃, and grinding into powder to obtain the functional hybrid material.
S2: grinding the obtained functional hybrid material and 2.2g of Benzotriazole (BTA) into powder, adding water, mixing uniformly, vacuum filtering under the condition that the display value of a pressure gauge is-0.1 MPa, and drying at 80 ℃ to obtain the composite functional hybrid material.
S3: dissolving 2.98g of zinc sulfate (the molar ratio of the zinc sulfate to the benzotriazole is 1). An electron microscope photograph of the antibacterial nanocomposite C1 was taken to observe a local structure, as shown in FIG. 1, the antibacterial nanocomposite C1 had a stable structure, and was approximately spherical, and the particle diameter of the antibacterial nanocomposite C1 was measured to be 300 to 700nm.
(II) detection of antibacterial Property of antibacterial nanocomposite C1
Antibacterial testing is carried out on the antibacterial nano composite material C1 (namely BTA-ZnO-PHMG @ TM) according to GB/T21510-2008 'detection method for antibacterial performance of nano inorganic material', wherein the result of one-time antibacterial testing is shown in figure 2, the detection result of colony forming units of each bacterium is marked below a flat plate in figure 2, the antibacterial nano composite material shows a lasting antibacterial effect along with the time extension, and when the antibacterial nano composite material is added for 30min, escherichia coli is completely inhibited; after the antibacterial nano composite material is added for 20min, no staphylococcus aureus and candida albicans survive, which shows that BTA-ZnO-PHMG @ TM has outstanding long-acting antibacterial effect on escherichia coli and staphylococcus aureus with different colony forming units. After repeated tests, the average value is taken, and the results show that the antibacterial rate of the BTA-ZnO-PHMG @ TM to escherichia coli is more than 99%, the antibacterial rate to staphylococcus aureus is more than 99%, and the antibacterial rate to candida albicans is more than 90%.
Examples 2-6 preparation of antibacterial nanocomposites
Examples 2 to 6 are methods for preparing an antibacterial nanocomposite, and the specific methods are substantially the same as those in example 1, except that the parameter settings are different, and the specific differences are shown in table 1:
wherein, in the organic macromolecule antibacterial agent containing guanidyl, polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride and polyhexamethylene guanidine phosphate are marked with codes of x, y and z in sequence;
table 1 table of parameters of examples 2-6
The other parts of examples 2 to 6 are the same as in example 1 or are common general knowledge to the person skilled in the art.
Transmission electron micrographs of the antibacterial nanocomposites C1-C6 were taken and tested for antibacterial performance according to the method of example 1. The results show that the antibacterial nano composite materials C1-C6 are stable in structure and nearly spherical, and the particle diameter is 300-700nm through measurement; the antibacterial detection result shows that the antibacterial rate to escherichia coli is more than 99%, the antibacterial rate to staphylococcus aureus is more than 99%, and the antibacterial rate to candida albicans is more than 90%.
Example 7 application of antibacterial nanocomposite to preparation of antibacterial fiber material
In this example, the antibacterial nanocomposite C1 obtained in example 1 and polyamide 56 resin (organic polymer material) are uniformly mixed according to a mass ratio of 3.
Compared with the mode of coating the antibacterial fiber material on the surface of the fiber material, the antibacterial fiber material prepared by the invention has the advantages that the antibacterial effect is durable due to the accurate addition amount.
Example 8 comparison of antibacterial Effect of antibacterial nanocomposite
Referring to example 1, the antibacterial test of E.coli was performed on equivalent amounts of TM, znO-TM, PHMG-TM and BTA-ZnO-PHMG @ TM according to GB/T21510-2008 "method for detecting antibacterial properties of Nano inorganic Material", and the results are shown in FIG. 3.
Wherein, each detection object and the preparation method are as follows: BTA-ZnO-PHMG @ TM was prepared from example 1; TM is porous tourmaline prepared from example 1; the preparation method of ZnO-TM is the same as that of example 1 except that PHMG and BTA are not added; the PHMG-TM was prepared in the same manner as in example 1 except that the metal salt and BTA were not added;
the detection result is shown in FIG. 3, and compared with TM, znO-TM and PHMG-TM, the BTA-ZnO-PHMG @ TM prepared by the invention has the best antibacterial effect. Shows that the porous tourmaline, the organic high molecular antibacterial agent containing guanidyl, benzotriazole and metal salt have synergistic interaction and jointly improve the antibacterial effect.
Example 9 Long-lasting antibacterial Effect of antibacterial nanocomposite
The PHMG has high-efficiency bactericidal performance, and the longer the PHMG is kept in the composite material, the longer the antibacterial performance of the composite material is kept. Respectively dispersing equal amounts of PHMG, PHMG-TM and BTA-ZnO-PHMG @ TM in water, detecting the content of PHMG in water by detecting pH value, and representing the release rate of PHMG, thereby judging the retention rate of PHMG in the composite material.
As shown in FIG. 4, compared with other materials, BTA-ZnO-PHMG @ TM is soaked in water for a long time, but the release rate of PHMG is kept at a lower level, which shows that the protective sealing film on the surface of BTA-ZnO-PHMG @ TM is lasting and effective, and can ensure the slow release of PHMG, thereby realizing long-acting antibiosis.
Although the present invention has been described in detail with reference to the above embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. The preparation process of nanometer composite antibacterial material features that porous tourmaline as carrier is loaded with guanidyl-containing organic polymer antibacterial agent to obtain functional hybrid material, which is crushed and then surface sealed with benzotriazole and metal salt solution.
2. The method of preparing an antimicrobial nanocomposite according to claim 1, comprising the following steps performed in sequence:
s1, taking porous tourmaline and organic polymer antibacterial agent solution containing guanidyl, performing ultrasonic treatment, and placing in a vacuum environment to obtain a functional hybrid material;
s2, grinding the functional hybrid material and benzotriazole into powder, adding water, mixing uniformly, carrying out vacuum filtration at 80-90 ℃, and drying to obtain a composite functional hybrid material;
and S3, adding the composite functional hybrid material into a metal salt solution, standing for 1-2h, washing, carrying out vacuum filtration, drying and carrying out ultraviolet irradiation to obtain the antibacterial nano composite material.
3. The method for preparing antibacterial nanocomposite material according to claim 2, wherein the porous tourmaline is obtained by acidifying tourmaline, washing, vacuum-filtering, and drying;
the display value of the pressure gauge in the vacuum environment is-0.1 to-0.02 MPa, and the time for placing the pressure gauge in the vacuum environment is 1 to 3 hours;
the display value of a pressure gauge during vacuum filtration is-0.1 to-0.02 MPa, and the filtration time is 1 to 5min;
the solvents of the guanidino-containing organic polymer antibacterial agent solution and the metal salt solution are water;
the water flow speed of the washing is 50-100m/s;
the ultraviolet wavelength of the ultraviolet irradiation is 185-254nm, and the irradiation time is 10-30min.
4. The method of claim 3, wherein the acidifying is carried out by treating the tourmaline with sulfuric acid to 60-80% of the mass before treatment.
5. The method for preparing antibacterial nanocomposite material according to claim 4, wherein the mass ratio of the porous tourmaline, the guanidyl-containing organic polymer antibacterial agent and the metal salt is 1-10:1:1-10.
6. The method of claim 5, wherein the molar ratio of metal salt to benzotriazole is 1:1-3.
7. The method of preparing an antibacterial nanocomposite as claimed in any one of claims 1 to 6, wherein the guanidino-containing organic polymeric antibacterial agent is at least one of polyhexamethyleneguanidine hydrochloride, polyhexamethylenebiguanide hydrochloride and polyhexamethyleneguanidine phosphate.
8. The method of preparing an antibacterial nanocomposite as claimed in claim 7, wherein the metal salt is at least one of copper chloride, copper sulfate, silver nitrate, zinc sulfate, magnesium sulfate and zinc chloride.
9. The method of preparing an antibacterial nanocomposite material according to any one of claims 1 to 6 or 8, wherein the antibacterial nanocomposite material has a particle diameter of 300 to 700nm.
10. Use of the method of preparation of antibacterial nanocomposite material according to any of claims 1 to 9 as antibacterial material for coatings, textiles, protective articles, medical materials, plastic ware, digital products and household electrical appliances.
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| CN202211141827.5A CN115399333B (en) | 2022-09-20 | 2022-09-20 | Preparation method and application of antibacterial nanocomposite |
| PCT/CN2022/123080 WO2024060307A1 (en) | 2022-09-20 | 2022-09-30 | Preparation method for antibacterial nanocomposite material and use thereof |
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| CN104631115A (en) * | 2013-11-15 | 2015-05-20 | 青岛鑫益发工贸有限公司 | Antibacterial anti-odor finishing application technology for textiles |
| CN110354304A (en) * | 2019-07-29 | 2019-10-22 | 湖州市中心医院 | Substrate and its preparation process for prosthese after artificial joint replacement |
| CN112853747A (en) * | 2021-02-26 | 2021-05-28 | 石家庄学院 | Preparation method of long-acting antibacterial polyester fiber based on composite nano silver and special device thereof |
| CN112998884A (en) * | 2021-02-24 | 2021-06-22 | 吉林大学 | Long-acting antibacterial material, dental diaphragm and long-acting invisible appliance |
| CN113801457A (en) * | 2021-10-16 | 2021-12-17 | 福州大学 | Efficient antibacterial polycarbonate composite material and preparation method thereof |
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| CN101112199A (en) * | 2007-09-06 | 2008-01-30 | 哈尔滨工业大学 | Sulfate reduction-resisting bacteria powder preparation adopting silver-carrying verdelite and method for preparing the same |
| JP2009084174A (en) * | 2007-09-28 | 2009-04-23 | Nippon Chem Ind Co Ltd | Antibacterial agent |
| CN105670238A (en) * | 2014-11-21 | 2016-06-15 | 宁波康氏塑料科技有限公司 | Sterilizing polyester resin |
| CN105801976B (en) * | 2016-04-24 | 2017-12-26 | 广东辉源卫浴科技有限公司 | A kind of HDPE antibiotic plastics and preparation method thereof |
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| CN104631115A (en) * | 2013-11-15 | 2015-05-20 | 青岛鑫益发工贸有限公司 | Antibacterial anti-odor finishing application technology for textiles |
| CN110354304A (en) * | 2019-07-29 | 2019-10-22 | 湖州市中心医院 | Substrate and its preparation process for prosthese after artificial joint replacement |
| CN112998884A (en) * | 2021-02-24 | 2021-06-22 | 吉林大学 | Long-acting antibacterial material, dental diaphragm and long-acting invisible appliance |
| CN112853747A (en) * | 2021-02-26 | 2021-05-28 | 石家庄学院 | Preparation method of long-acting antibacterial polyester fiber based on composite nano silver and special device thereof |
| CN113801457A (en) * | 2021-10-16 | 2021-12-17 | 福州大学 | Efficient antibacterial polycarbonate composite material and preparation method thereof |
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| 莫尊理;王雅雯;胡惹惹;: "电气石功能复合材料的研究进展" * |
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| WO2024060307A1 (en) | 2024-03-28 |
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