CN112913857A - Nano-copper antibacterial material, antibacterial coating, and preparation method and application thereof - Google Patents

Nano-copper antibacterial material, antibacterial coating, and preparation method and application thereof Download PDF

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CN112913857A
CN112913857A CN202110080682.1A CN202110080682A CN112913857A CN 112913857 A CN112913857 A CN 112913857A CN 202110080682 A CN202110080682 A CN 202110080682A CN 112913857 A CN112913857 A CN 112913857A
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copper
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reducing agent
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周红岩
张红岩
杨莉
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • A01N59/20Copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides

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Abstract

The invention discloses a nano-copper antibacterial material, an antibacterial coating, and a preparation method and application thereof. Respectively dissolving soluble copper salt and a reducing agent in a solvent to obtain a homogeneous copper salt solution and a homogeneous reducing agent solution; and simultaneously pumping the copper salt solution and the reducing agent solution into the microchannel reaction tube in a hot bath state, reacting for 0.5-30 min at the temperature of 30-90 ℃ in the tube, and continuously pumping out a reaction product in the reaction tube, namely the uniformly dispersed nano copper antibacterial material. The nano copper antibacterial material can be further prepared into an antibacterial coating to be applied to a coating which can inhibit the growth of bacteria or kill the bacteria on the surface of a base material. The preparation of the antibacterial coating is simple, the nano-copper antibacterial material obtained in the continuous preparation process can be directly applied to the formula of the antibacterial coating without separation, the three-waste pollution and the safety risk caused by the operations of shutdown, separation, washing and the like of the traditional intermittent preparation method are avoided, and the industrial application is facilitated.

Description

Nano-copper antibacterial material, antibacterial coating, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a nano-copper antibacterial material, a continuous preparation method and application thereof, and an antibacterial coating, and a preparation method and application thereof.
Background
The invention and application of antibiotics are important means for inhibiting the growth of bacteria or killing bacteria at present, but due to the wide use and abuse of antibiotics, the generation of resistance of bacteria to antibiotics has become a common phenomenon, and various infectious diseases become the biggest health challenge facing the world again; in addition, conventional antibacterial agents not only develop multidrug resistance, but also cause various adverse side effects. Therefore, the demand for other alternative antibacterial technologies and materials is urgent, and inorganic metal materials are receiving attention from all over due to their high-efficiency broad-spectrum antibacterial ability, and particularly, copper preparations have been successfully applied to the field of pesticides and achieved a lot of achievements due to their advantages of no pollution, no residue and no drug resistance, and have great potential to become high-efficiency and low-cost antibacterial materials. More importantly, as one of the trace elements essential to human body, the low toxicity of copper has incomparable advantages for the application of copper in biomedical fields (ACS appl. Mater. interfaces 2016,8, 16584-16594; 2019, 11, 73-83). Furthermore, the nano-copper material has better antibacterial ability due to its extremely high specific surface area and small size (Trends in Biotechnology 2012,30, 499-511).
The main method for preparing the nano copper material is a batch method at present, but the method has long reaction time and needs post-treatment steps such as separation, drying and the like. According to the Chinese patent CN201110009443.3, a copper precursor and organic alcohol are sealed in a high-pressure reaction kettle through an electrochemical method, the reaction is carried out for 2-3 hours at the high temperature of 200 ℃ and under the atmospheric pressure of 30 ℃, and then the nano copper powder is prepared through the steps of centrifugal separation, drying and the like. Xuedong Wu et al (Green chem.,2011,13,900) react for 16 hours at 80 ℃ with copper chloride as a raw material and citric acid as a catalyst, and nano-copper particles are obtained at 8000 rpm. Chinese patent CN201910999944.7 reports a preparation method of oil-soluble nano-copper, which comprises the steps of mixing a copper precursor with an organic modifier, reacting for 0.5-3 h at 20-80 ℃, adjusting the pH value to 7-9, adding a reducing agent at 20-85 ℃ for reacting for 0.5-24 h to obtain an oil-soluble nano-copper reaction solution, and carrying out reduced pressure distillation to obtain the nano-copper. However, the above methods all have the problems of complicated process, long reaction time, easy generation of three wastes in the post-treatment process and the like, and in addition, the above methods all have the defects of long reaction time, large equipment volume and the like due to batch preparation in a batch reaction kettle.
In view of the above, the technical problem to be solved in the art is to provide a method for continuously preparing a nano copper antibacterial material with simple method and low cost.
Disclosure of Invention
The invention aims to provide a preparation method of a nano-copper antibacterial material, and aims to solve the problems of complex process, long reaction time, three wastes in post-treatment process and the like in the prior art.
The invention also aims to provide the nano-copper antibacterial material obtained by the preparation method.
The invention also aims to provide the application of the nano-copper antibacterial material in an antibacterial product for inhibiting the growth of bacteria or killing the bacteria.
Still another object of the present invention is to provide an antibacterial paint prepared based on the above nano-copper antibacterial material.
The invention further aims to provide a preparation method and application of the antibacterial coating.
The invention is realized in such a way that a preparation method of a nano-copper antibacterial material comprises the following steps:
(1) respectively dissolving soluble copper salt and a reducing agent in a solvent (the dosage of the solvent is based on the total dissolved solute) to obtain a homogeneous copper salt solution and a homogeneous reducing agent solution; wherein the reducing agent is one of ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride; the solvent is one of water, ethanol and methanol;
(2) mixing and pumping the copper salt solution and the reducing agent solution obtained in the step (1) into a microchannel reaction tube in a hot bath state, reacting for 0.5-30 min at 30-90 ℃ in the tube, and continuously pumping out a reaction product in the reaction tube to obtain a uniformly dispersed nano copper antibacterial material; wherein the molar ratio of soluble copper salt contained in the copper salt solution to reducing agent contained in the reducing agent solution is 1: (0.8-2).
Preferably, in the step (1), the soluble copper salt is one of copper chloride, copper sulfate, copper nitrate and hydrates thereof.
Preferably, in step (2), the molar ratio of the copper salt solution to the reducing agent of the reducing agent solution is 1: (1.2-1.5).
Preferably, in the step (2), the microchannel reaction tube is a spiral stainless steel tube, and the inner diameter of the tube is 0.5-5 mm (the length of the tube is 0.5-40 m); the flow rate of the solution in the reaction tube is 0.05-5 mL/min.
Preferably, in the step (2), the reaction flow rate is 0.06-2 mL/min.
The invention further discloses a nano-copper antibacterial material obtained by the preparation method, which comprises the following steps:
(1) respectively dissolving soluble copper salt and a reducing agent in a solvent to obtain a homogeneous copper salt solution and a homogeneous reducing agent solution; wherein the reducing agent is one of ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride; the solvent is one of water, ethanol and methanol;
(2) mixing the copper salt solution obtained in the step (1) and a reducing agent solution, pumping into a microchannel reaction tube in a hot bath state, reacting for 0.5-30 min at 30-90 ℃ in the tube, and continuously obtaining uniformly dispersed nano-copper antibacterial materials in the pumping-out process; wherein the molar ratio of the copper salt solution to the reducing agent of the reducing agent solution is 1: (0.8-2).
The invention further discloses application of the nano-copper antibacterial material in an antibacterial product for inhibiting the growth of bacteria or killing the bacteria.
The invention further discloses an antibacterial coating, which comprises the following components in parts by mass:
1 part of nano-copper antibacterial material;
40-80 parts of water-based epoxy resin;
20-40 parts of a curing agent.
Preferably, the mass part of the water-based epoxy resin is 50-60 parts.
The invention further discloses application of the antibacterial coating as a coating for inhibiting bacterial growth or killing bacteria on the surface of a base material.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
(1) compared with the existing intermittent preparation process, the method for preparing the nano-copper antibacterial material through the microchannel reaction tube has the advantages that the equipment is simpler, the operation is simple, the safety is high, the characteristics of high microchannel heating efficiency, uniform reactant heating and no back mixing are utilized, the continuous output and the uninterrupted amplification production can be carried out, the reaction time can be obviously shortened, the uniformity of the nano-antibacterial material is improved, the flux is high, and the stability of the performance of subsequent application products is better;
(2) the preparation of the antibacterial coating is simple, the nano-copper antibacterial material obtained in the continuous preparation process can be directly applied to the formula of the antibacterial coating without separation, the three-waste pollution and the safety risk caused by the operations of shutdown, separation, washing and the like of the traditional intermittent preparation method are avoided, and the industrial application is facilitated.
Drawings
FIG. 1 is a schematic reaction flow diagram of the nano-copper antibacterial material of the present invention; wherein, 1 is a sample feeding pump, and 2 is a microchannel reaction tube provided with a hot bath;
FIG. 2 is a photograph of nano-copper antibacterial materials 1 to 3 prepared in examples 1 to 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation process of the nano-copper antibacterial material in the following embodiment of the invention is as shown in fig. 1, wherein two pumps 1 are respectively installed on a pipeline, the liquid inlet end of each pipeline is respectively connected with a copper salt solution and a reducing agent solution, the liquid outlet ends of the two pipelines are connected with the liquid inlet end of a microchannel reaction tube through a three-way valve, the microchannel reaction tube is a hollow tube with two open ends and is in a spiral shape, the main body of the reaction tube is placed in an oil bath or water bath environment 2 to heat the inside of the tube to a required temperature, and the liquid outlet end of the reaction tube is a continuous outlet end of a reaction product.
Example 1
(1) Dissolving 50mmol of copper chloride dihydrate in 50mL of ethanol to obtain a copper salt solution, and dissolving 60mmol of sodium hypophosphite as a reducing agent in 50mL of ethanol to obtain a reducing agent solution;
(2) pumping the copper salt solution and the reducing agent solution into a microchannel reaction tube with the inner diameter of 2mm at the flow rate of 0.08mL/min by a sample injection pump, and staying at 65 ℃ for 6min (the staying time is determined by the length and the inner diameter of the tube and the flow rate of the mixed solution, and the same is carried out below), so as to obtain a uniformly dispersed nano copper antibacterial material 1;
(3) mixing the nano-copper antibacterial material 1 and water-based epoxy resin (F0704) according to a mass ratio of 1: 60, adding 30 parts by mass of a curing agent according to a commercial formula of epoxy resin, stirring to obtain an antibacterial coating 1, coating the coating 1 on an aluminum alloy substrate, and curing at room temperature to obtain the antibacterial coating 1. The waterborne epoxy resin and the matched curing agent are purchased from Shenzhen Jitian chemical industry Co., Ltd, the same below.
Example 2
(1) Dissolving 50mmol of copper nitrate in 50mL of water to obtain a copper salt solution, and dissolving 70mmol of tetrabutylammonium borohydride as a reducing agent in 50mL of water to obtain a reducing agent solution;
(2) pumping the copper salt solution and the reducing agent solution into a microchannel reaction tube with the inner diameter of 3.5mm at the flow rate of 0.06mL/min by a sample injection pump, and staying for 8min at the temperature of 90 ℃ to obtain a uniformly dispersed nano copper antibacterial material 2;
(3) mixing the nano-copper antibacterial material 2 and water-based epoxy resin (F0704) according to a mass ratio of 1: 50, adding 10 parts by mass of curing agent and 20 parts by mass of defoaming agent according to a commercial formula of epoxy resin, stirring to obtain an antibacterial coating 2, coating the coating 2 on a carbon steel substrate, and curing at room temperature to obtain the antibacterial coating 2.
Example 3
(1) Dissolving 50mmol of copper sulfate pentahydrate in 50mL of methanol to obtain a copper salt solution, and dissolving 65mmol of ascorbic acid as a reducing agent in 50mL of methanol to obtain a reducing agent solution;
(2) pumping the copper salt solution and the reducing agent solution into a microchannel reaction tube with the inner diameter of 34mm at the flow rate of 2mL/min by a sample injection pump, and staying at 50 ℃ for 10min to obtain a uniformly dispersed nano-copper antibacterial material 3;
(4) mixing the nano-copper antibacterial material 3 and the water-based epoxy resin (F0704) according to a mass ratio of 1: 45, adding 30 parts by mass of a curing agent according to a commercial formula of epoxy resin, stirring to obtain an antibacterial coating 3, coating the coating 3 on a tinplate base material, and curing at room temperature to obtain the antibacterial coating 3.
Example 4
(1) Dissolving 50mmol of copper sulfate pentahydrate in 30mL of water to obtain a copper salt solution, and dissolving 100mmol of ascorbic acid as a reducing agent in 80mL of ethanol to obtain a reducing agent solution;
(2) pumping the copper salt solution and the reducing agent solution into a microchannel reaction tube with the inner diameter of 5mm at the flow rate of 5mL/min by a sample injection pump, and staying at 90 ℃ for 10min to obtain a uniformly dispersed nano-copper antibacterial material 4;
(4) mixing the nano-copper antibacterial material 3 and the water-based epoxy resin (F0704) according to a mass ratio of 1: 40, adding 40 parts by mass of the epoxy resin according to a commercial formula, stirring to obtain an antibacterial coating 4, coating the coating 4 on a tinplate base material, and curing at room temperature to obtain the antibacterial coating 4.
Example 5
(1) Dissolving 50mmol of copper sulfate pentahydrate in 80mL of ethanol to obtain a copper salt solution, and dissolving 40mmol of ascorbic acid as a reducing agent in 30mL of water to obtain a reducing agent solution;
(2) pumping the copper salt solution and the reducing agent solution into a microchannel reaction tube with the inner diameter of 0.5mm at the flow rate of 0.05mL/min by using a sample injection pump, and staying for 30min at the temperature of 30 ℃ to obtain a uniformly dispersed nano copper antibacterial material 5;
(4) mixing the nano-copper antibacterial material 5 and the water-based epoxy resin (F0704) according to a mass ratio of 1: 80, adding 20 parts by mass of curing agent according to a commercial formula of epoxy resin, stirring to obtain the antibacterial coating 5, coating the coating 5 on a tinplate base material, and curing at room temperature to obtain the antibacterial coating 5.
Effects of the embodiment
1. Observation of the appearance of the nano-copper antibacterial materials 1 to 3 prepared in the above examples 1 to 3
The observation result is shown in fig. 2, wherein 1, 2 and 3 correspond to the nano-copper antibacterial material 1, the nano-copper antibacterial material 2 and the nano-copper antibacterial material 3 respectively; as can be seen from the figure, the nano-copper in each nano-copper antibacterial material is stably dispersed in the solvent.
2. Liquid drop method for testing antibacterial effect
The antimicrobial properties of the antimicrobial coatings 1-3 prepared in examples 1-3 above were tested by the liquid drop method
Applied Materials according to ACS&Interfaces, 2019, 11(11), 73-83, inoculating S.aureus and P.aeruginosa in a suitable medium, controlled at 37 ℃ for 18-24 hours in a shake flask incubator. The bacterial suspension was centrifuged at 2700rpm for 8 minutes, washed with Phosphate Buffered Saline (PBS), and then re-dispersed in PBS at a concentration of-107/mL. The concentration of bacteria in PBS was determined by measuring the optical density of the suspension by a microplate reader (Multiskan GO, Thermo Scientific, USA), reading 0.1 at 540nm, corresponding to a concentration of-108one/mL. Cutting 1X 1cm2The different coating samples are respectively put into a 24-hole plate, sterilized by a 30W ultraviolet lamp for 20min and put into a biological safety cabinet. mu.L of bacterial suspension (containing 10)4one/mL) was dropped on the surface of the sample at 25 ℃ for 30 minutesA clock. Soaking the sample in 2mL PBS, ultrasonic processing for 4min, taking 100 μ L dispersion, spreading on the culture medium plate, culturing at 37 deg.C for 24h, counting the number of colonies, and calculating the reduction percentage of the number of colonies to the number of colonies on the blank medium, if no colonies are formed in three repeated tests, the expected antibacterial ability>99.8%。
2. Results
As shown in Table 1 below, Table 1 lists the performance test data for the samples prepared in examples 1-3:
table 1 performance test data results
Figure BDA0002909161370000071
Figure BDA0002909161370000081
As can be seen from the data in Table 1, the coatings prepared according to the present invention have good antimicrobial properties.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A preparation method of a nano-copper antibacterial material is characterized by comprising the following steps:
(1) respectively dissolving soluble copper salt and a reducing agent in a solvent to obtain a homogeneous copper salt solution and a homogeneous reducing agent solution; wherein the reducing agent is one of ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride; the solvent is one of water, ethanol and methanol;
(2) pumping the copper salt solution and the reducing agent solution obtained in the step (1) into a microchannel reaction tube in a hot bath state at the same time, reacting for 0.5-30 min at 30-90 ℃ in the tube, and continuously pumping out a reaction product in the reaction tube to obtain a uniformly dispersed nano copper antibacterial material; wherein the molar ratio of soluble copper salt contained in the copper salt solution to reducing agent contained in the reducing agent solution is 1: (0.8-2).
2. The method of preparing nano-copper antibacterial material according to claim 1, wherein in the step (1), the soluble copper salt is one of copper chloride, copper sulfate, copper nitrate and hydrates thereof.
3. The method for preparing nano-copper antibacterial material according to claim 1, wherein in the step (2), the molar ratio of the copper salt in the copper salt solution to the reducing agent in the reducing agent solution is 1: (1.2-1.5).
4. The method for preparing nano-copper antibacterial material according to claim 1, wherein in the step (2), the microchannel reaction tube is a spiral stainless steel tube, the inner diameter of the tube is 0.5-5 mm, and the flow rate of the solution in the reaction tube is 0.05-5 mL/min.
5. The method for preparing nano-copper antibacterial material according to claim 4, wherein in the step (2), the reaction flow rate is 0.06-2 mL/min.
6. The nano-copper antibacterial material obtained by the preparation method of any one of claims 1 to 5.
7. Use of the nano-copper antibacterial material of claim 6 as an antibacterial product for inhibiting the growth of bacteria or killing bacteria.
8. The antibacterial coating is characterized by comprising the following components in parts by mass:
1 part of the nano-copper antibacterial material of claim 6;
40-80 parts of water-based epoxy resin;
20-40 parts of a curing agent.
9. The antibacterial coating according to claim 8, wherein the mass part of the water-based epoxy resin is 50 to 60 parts.
10. Use of an antimicrobial coating according to claim 8 or claim 9 as a coating on a substrate surface to inhibit bacterial growth or kill bacteria.
CN202110080682.1A 2021-01-21 2021-01-21 Nano-copper antibacterial material, antibacterial coating, and preparation method and application thereof Pending CN112913857A (en)

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主编:张明: "《纳米与新材料专辑 Ⅲ》", 25 October 2004, 材料报道社 *

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* Cited by examiner, † Cited by third party
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CN113956732A (en) * 2021-11-22 2022-01-21 四川三棵树涂料有限公司 Stain-resistant, odor-free, environment-friendly, antibacterial and antiviral shell paint and preparation method thereof
CN115281215A (en) * 2022-07-05 2022-11-04 国科温州研究院(温州生物材料与工程研究所) Copper-zinc doped phosphate antibacterial agent, preparation method thereof and application thereof in antibacterial plastics
CN115232534A (en) * 2022-08-26 2022-10-25 侯晓娜 Antibacterial anticorrosive paint and preparation method thereof

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