CN110973132A - Hydrophobic antibacterial mildew-proof material and preparation method and application thereof - Google Patents
Hydrophobic antibacterial mildew-proof material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110973132A CN110973132A CN201911304359.7A CN201911304359A CN110973132A CN 110973132 A CN110973132 A CN 110973132A CN 201911304359 A CN201911304359 A CN 201911304359A CN 110973132 A CN110973132 A CN 110973132A
- Authority
- CN
- China
- Prior art keywords
- hydrophobic
- organic framework
- metal organic
- acid
- framework material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/48—Nitro-carboxylic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a hydrophobic antibacterial mildew-proof material, a preparation method and application thereof, comprising a metal organic framework material and a hydrophobic agent dispersed in the metal organic framework material; the metal organic framework material comprises any one or the combination of at least two of a copper-based metal organic framework material, a zinc-based metal organic framework material, a magnesium-based metal organic framework material or a silver-based metal organic framework material. The hydrophobic antibacterial mildew-proof material provided by the invention has a higher specific surface area, contains higher antibacterial ion content, can better adsorb microorganisms, and has a more excellent antibacterial effect; in addition, the hydrophobic antibacterial mildew-proof material provided by the invention has excellent hydrophobic property, and can avoid the defects of bacterial growth and material mildew caused by the humid use environment.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to a hydrophobic antibacterial mildewproof material, and a preparation method and application thereof.
Background
Metal Organic Framework (MOFs) are crystalline porous materials with periodic network structures formed by connecting inorganic Metal centers (Metal ions or Metal clusters) and bridged organic ligands through self-assembly. MOFs are an organic-inorganic hybrid material, also called coordination polymer (coordination polymer), which is different from inorganic porous materials and from general organic complexes. Most of the metal organic frameworks have high porosity and good chemical stability; because of the ability to control pore structure and large specific surface area, MOFs have broader application prospects than other porous materials.
CN105401245A discloses a method for preparing copper oxide antibacterial fiber, comprising: 1) uniformly mixing copper oxide powder, a silicon-containing surfactant and polyester chips to prepare functional master batches; the powder of the copper oxide is directly less than 0.8 mu m; 2) and mixing the functional master batches and the polyester chips according to a certain mass ratio, and adding the mixture into a screw extruder for spinning to obtain the copper-containing antibacterial fiber. The fabric provided by the patent application has certain antibacterial property, but the antibacterial fiber produced by adopting copper oxide as a raw material has higher requirement on the treatment of wastewater in the production process, and the cost is increased. CN107315043A discloses a nickel metal organic framework nano material and application thereof, the preparation method is that a glycol solution of divalent nickel salt and a dimethylformamide solution of terephthalic acid are mixed, after being evenly stirred, hydrothermal reaction is carried out at the temperature of 150-; washing the precipitate with dimethylformamide and ethanol, and drying to obtain the nickel metal organic framework nano material. The nickel metal organic framework nano material provided by the patent application can be applied to the preparation of a sensor electrode for detecting glucose.
The metal organic framework materials studied at present are basically applied to the adsorption separation of H2The fields of catalysts, magnetic materials, optical materials and the like, and other fields are not related to too much. Therefore, it is desired to develop a method applicable toThe application of the metal organic framework material in the field of antibiosis and mildew prevention is enriched.
Disclosure of Invention
The invention aims to provide a hydrophobic antibacterial mildewproof material, and a preparation method and application thereof. The hydrophobic antibacterial mildew-proof material provided by the invention has a higher specific surface area, contains higher antibacterial ion content, can better adsorb microorganisms, and has a more excellent antibacterial effect; in addition, the hydrophobic antibacterial mildew-proof material provided by the invention has excellent hydrophobic property, and can avoid the defects of bacterial growth and material mildew caused by the humid use environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a hydrophobic antibacterial mildewproof material, which comprises a metal organic framework material and a hydrophobic agent dispersed in the metal organic framework material;
the metal organic framework material comprises any one or the combination of at least two of a copper-based metal organic framework material, a zinc-based metal organic framework material, a magnesium-based metal organic framework material or a silver-based metal organic framework material.
The metal organic framework material selected by the invention has higher porosity, larger specific surface area and uniformly dispersed active sites, so that the metal organic framework material can be used as a carrier to adsorb more antibacterial ions, namely the metal organic framework material provided by the invention has higher antibacterial metal ion content and larger specific surface area, can better adsorb microorganisms and obtains better antibacterial effect. Meanwhile, the hydrophobic antibacterial and mildewproof material contains the hydrophobic agent, so that the defects of bacterial growth and material mildew caused by material or environment humidity can be prevented while the material is sterilized.
The hydrophobic antibacterial mildew-proof material provided by the invention has excellent sterilization, hydrophobic and mildew-proof effects, so that the hydrophobic antibacterial mildew-proof material has potential application values in the aspects of antifouling, self-cleaning, antibacterial, mildew-proof and the like.
Preferably, the hydrophobic agent is selected from organic acid hydrophobic agents including any one or a combination of at least two of stearic acid, linoleic acid, linolenic acid, lauric acid or oleic acid.
In order to enable the hydrophobizing agent to be uniformly dispersed in the metal organic framework material, so that the final hydrophobic antibacterial mildew-proof material has a better hydrophobic effect, the organic acid hydrophobizing agent is preferably selected in the invention, and if other hydrophobizing agents are selected, such as fluorine-containing organic substance hydrophobizing agents, the possibility that the hydrophobizing agent is not uniformly dispersed in the metal organic framework material is caused, so that the hydrophobic property of the finally obtained hydrophobic antibacterial mildew-proof material is poor, and the subsequent application effect of the hydrophobic antibacterial mildew-proof material in a humid environment is further influenced.
Preferably, the mass ratio of the metal-organic framework material to the hydrophobizing agent is 100 (1-10), such as 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, and the like.
The mass ratio of the metal organic framework material to the hydrophobic agent needs to be within the limited range of the invention, if the content of the hydrophobic agent is too high, the hydrophobic agent can agglomerate and be dispersed unevenly in the metal organic framework material; if the content of the hydrophobizing agent is too low, the hydrophobicity is poor.
In the invention, the composition of the metal-organic framework material comprises an organic ligand, and the organic ligand is an organic acid.
Preferably, the organic acid is selected from phthalic acid and/or benzenetricarboxylic acid, and further preferably any one or a combination of at least two of 2, 5-dihydroxyterephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid or 2, 5-dinitro-1, 3, 4-benzenetricarboxylic acid.
In a second aspect, the present invention provides a method for preparing the hydrophobic antibacterial mildewproof material according to the first aspect, which comprises the following steps:
(1) mixing and crystallizing metal salt and organic ligand to obtain the metal organic framework material;
(2) and mixing the metal organic framework material with a hydrophobic agent, heating and drying to obtain the hydrophobic antibacterial mildewproof material.
Preferably, the mass ratio of the metal salt to the organic ligand is 1 (5-20), such as 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, and the like.
In the invention, the mass ratio of the metal salt to the organic ligand needs to be in the limited range of the invention, if the content of the organic ligand is too high, the metal ion load is insufficient, and the antibacterial performance of the material is poor; if the content of the organic ligand is too low, the mechanical property of the material is poor, and the application effect is poor.
Preferably, the metal salt consists of a metal cation and an anion.
Preferably, the metal cation is selected from any one of copper ion, zinc ion, magnesium ion or silver ion or a combination of at least two thereof.
Preferably, the anion comprises any one or a combination of at least two of sulfate, phosphate, chloride, iodide, sulfide or phosphate ions.
Preferably, the mixing of step (1) is carried out in a mixed solvent.
Preferably, the mixed solvent includes a combination of N, N-dimethylformamide, deionized water and anhydrous ethanol.
Preferably, the volume ratio of the N, N-dimethylformamide to the deionized water to the absolute ethyl alcohol is (0.5-1): 1-2):1, the 0.5-1 can be 0.6, 0.7, 0.8, 0.9 and the like, and the 1-2 can be 1.2, 1.4, 1.6, 1.8 and the like.
If the volume ratio of the mixed solvent is not within the range defined in the present invention, the hydrophobic property of the material may be poor.
Preferably, the mixing of step (1) is performed in ultrasound for a time of 15-90min, such as 20min, 30min, 40min, 50min, 60min, 70min, 80min, etc.
Preferably, the crystallization temperature is 100-150 ℃, such as 110 ℃, 120 ℃, 130 ℃, 140 ℃ and the like, and the time is 5-20h, such as 6h, 8h, 10h, 12h, 15h, 18h and the like.
Preferably, the step (1) further comprises filtering, washing and drying after crystallization.
Preferably, the washing comprises washing with N, N-dimethylformamide and then with anhydrous ethanol.
Preferably, the drying is carried out at a temperature of 80-150 ℃, e.g., 90 ℃, 100 ℃, 120 ℃, 140 ℃, etc., for a period of 6-12h, e.g., 7h, 8h, 9h, 10h, 11h, etc.
Preferably, the mixing of step (2) is performed in a solvent, which is absolute ethanol.
Preferably, the mixing in step (2) is ultrasonic mixing for 10-40min, such as 15min, 20min, 25min, 30min, 35min, etc.
Preferably, the heating temperature in step (2) is 100-150 ℃, such as 110, 120, 130, 140, etc., and the time is 1-5h, such as 2h, 3h, 4h, etc.
The invention selects mixing and heating, which can lead the hydrophobic agent to be dispersed evenly and have better bonding force with the organic framework material.
Preferably, the drying temperature in step (2) is 100-150 ℃, such as 110, 120, 130, 140, etc., and the time is 1-5h, such as 2h, 3h, 4h, etc.
In a third aspect, the present invention provides a use of the hydrophobic antimicrobial mould proof material according to the first aspect in an adsorbent, a catalyst or a hydrogen storage material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the metal organic framework material selected by the invention has higher porosity, larger specific surface area and uniformly dispersed active sites, so that the metal organic framework material can be used as a carrier to adsorb more antibacterial ions, namely the metal organic framework material provided by the invention has higher antibacterial metal ion content and larger specific surface area, can better adsorb microorganisms and obtains better antibacterial effect. Meanwhile, the hydrophobic antibacterial mildew-proof material contains a hydrophobic agent, so that the defects of bacterial growth and material mildew caused by material or environment humidity can be prevented while the material is sterilized;
(2) the hydrophobic antibacterial mildewproof material provided by the invention has excellent sterilizing, hydrophobic and mildewproof effects, wherein the specific surface area is 500m2·g-1Above, the diameter of the inhibition zone in the antibacterial and antifungal test is more than 9.5mm, and the water contact angle is more than 140 degrees.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A hydrophobic antibacterial mildew-resistant material is prepared by the following steps:
(1) preparation of copper-based metal organic framework materials (Cu-MOFs):
mixing 2.0g of copper nitrate, 30mL of 2, 5-dihydroxy terephthalic acid, 20mL of N, N-dimethylformamide, 20mL of deionized water and 20mL of absolute ethyl alcohol under ultrasound for 30min to obtain a dispersion liquid;
then pouring the dispersion liquid into a polytetrafluoroethylene kettle, putting the reaction kettle into a 130 ℃ oven for crystallization for 15 hours, taking out the reaction kettle, and filtering to obtain a blue product;
and washing the product twice with N, N-dimethylformamide to remove unreacted 2, 5-dihydroxyterephthalic acid, washing twice with ethanol, and finally drying in an oven at 120 ℃ for 12 hours to obtain the Cu-MOFs.
(2) Preparation of hydrophobic antibacterial mildewproof material
Weighing 10mL of absolute ethyl alcohol, pouring the absolute ethyl alcohol into a round-bottom flask, weighing 0.25g of stearic acid particles, adding the stearic acid particles into the round-bottom flask, and then magnetically stirring until the stearic acid particles are completely dissolved;
weighing 5g of Cu-MOFs material, adding the Cu-MOFs material into the round-bottom flask, and carrying out ultrasonic treatment for 20min to uniformly disperse the Cu-MOFs material so as to obtain a dispersion liquid;
then placing the round-bottom flask into a 110 ℃ oil bath kettle, heating and refluxing under magnetic stirring, stopping heating after 2 hours, and continuing stirring;
when the temperature of the suspension in the round-bottom flask is cooled to room temperature, the magnetic stirrer is closed; and then removing the solvent in a vacuum oven at 120 ℃ to obtain the hydrophobic antibacterial and mildewproof material.
Example 2
A hydrophobic antibacterial mildew-resistant material is prepared by the following steps:
(1) preparation of silver-based metal organic framework materials (Ag-MOFs):
mixing 2.0g of silver chloride, 40mL of 2-amino terephthalic acid, 10mL of LN, N-dimethylformamide, 20mL of deionized water and 20mL of absolute ethyl alcohol under ultrasound for 90min to obtain a dispersion liquid;
then pouring the dispersion liquid into a polytetrafluoroethylene kettle, putting the reaction kettle into a 120 ℃ oven for crystallization for 10 hours, taking out the reaction kettle, and filtering to obtain a silver product;
and washing the product twice with N, N-dimethylformamide to remove unreacted 2-amino terephthalic acid, washing twice with ethanol, and finally drying in an oven at 100 ℃ for 10 hours to obtain the Ag-MOFs.
(2) Preparation of hydrophobic antibacterial mildewproof material
Weighing 10mL of absolute ethyl alcohol, pouring the absolute ethyl alcohol into a round-bottom flask, weighing 0.25g of lauric acid particles, adding the lauric acid particles into the round-bottom flask, and then magnetically stirring until the stearic acid particles are completely dissolved;
weighing 10g of Ag-MOFs material, adding the Ag-MOFs material into the round-bottom flask, and carrying out ultrasonic treatment for 20min to uniformly disperse the Ag-MOFs material so as to obtain a dispersion liquid;
then placing the round-bottom flask into a 110 ℃ oil bath kettle, heating and refluxing under magnetic stirring, stopping heating after 2 hours, and continuing stirring;
when the temperature of the suspension in the round-bottom flask is cooled to room temperature, the magnetic stirrer is closed; and then removing the solvent in a vacuum oven at 120 ℃ to obtain the hydrophobic antibacterial and mildewproof material.
Example 3
A hydrophobic antibacterial mildew-resistant material is prepared by the following steps:
(1) preparation of zinc-based metal organic framework materials (Zn-MOFs):
mixing 2.0g of zinc chloride, 10mL of 2, 5-dinitro-1, 3, 4-benzene tricarboxylic acid, 20mL of N, N-dimethylformamide, 40mL of deionized water and 20mL of absolute ethyl alcohol under ultrasound for 15min to obtain a dispersion liquid;
then pouring the dispersion liquid into a polytetrafluoroethylene kettle, putting the reaction kettle into a drying oven at 100 ℃ for crystallization for 20 hours, taking out the reaction kettle, and filtering to obtain a silver product;
and washing the product twice with N, N-dimethylformamide to remove unreacted 2-amino terephthalic acid, washing twice with ethanol, and finally drying in an oven at 150 ℃ for 6 hours to obtain the Zn-MOFs.
(2) Preparation of hydrophobic antibacterial mildewproof material
Weighing 10mL of absolute ethyl alcohol, pouring the absolute ethyl alcohol into a round-bottom flask, weighing 1g of linolenic acid particles, adding the linolenic acid particles into the round-bottom flask, and then magnetically stirring until stearic acid particles are completely dissolved;
weighing 10g of Zn-MOFs material, adding the Zn-MOFs material into the round-bottom flask, and carrying out ultrasonic treatment for 40min to uniformly disperse the Zn-MOFs to obtain a dispersion liquid;
then placing the round-bottom flask into a 100 ℃ oil bath kettle, heating and refluxing under magnetic stirring, stopping heating after 5 hours, and continuing stirring;
when the temperature of the suspension in the round-bottom flask is cooled to room temperature, the magnetic stirrer is closed; and then removing the solvent in a vacuum oven at 150 ℃ to obtain the hydrophobic antibacterial and mildewproof material.
Example 4
A hydrophobic antibacterial mildew-resistant material is prepared by the following steps:
(1) preparation of magnesium-based metal organic framework materials (Mg-MOFs):
mixing 2.0g of silver magnesium, 35mL of 2-nitroterephthalic acid, 10mL of N, N-dimethylformamide, 20mL of deionized water and 20mL of absolute ethyl alcohol under ultrasound for 40min to obtain a dispersion liquid;
then pouring the dispersion liquid into a polytetrafluoroethylene kettle, putting the reaction kettle into a drying oven at 150 ℃ for crystallization for 5 hours, taking out the reaction kettle, and filtering to obtain a silver product;
and washing the product twice with N, N-dimethylformamide to remove unreacted 2-amino terephthalic acid, washing twice with ethanol, and finally drying in an oven at 80 ℃ for 12 hours to obtain Mg-MOFs.
(2) Preparation of hydrophobic antibacterial mildewproof material
Weighing 10mL of absolute ethyl alcohol, pouring the absolute ethyl alcohol into a round-bottom flask, weighing 0.1g of linoleic acid particles, adding the linoleic acid particles into the round-bottom flask, and then magnetically stirring until the stearic acid particles are completely dissolved;
weighing 10g of Mg-MOFs material, adding the Mg-MOFs material into the round-bottom flask, and carrying out ultrasonic treatment for 10min to uniformly disperse the Mg-MOFs to obtain a dispersion liquid;
then placing the round-bottom flask into a 150 ℃ oil bath kettle, heating and refluxing under magnetic stirring, stopping heating after 1h, and continuing stirring;
when the temperature of the suspension in the round-bottom flask is cooled to room temperature, the magnetic stirrer is closed; and then removing the solvent in a vacuum oven at 100 ℃ to obtain the hydrophobic antibacterial and mildewproof material.
Comparative example 1
The difference from example 1 is that in step (2), no stearic acid particles are added, and a hydrophobic antibacterial and antifungal material is prepared.
Comparative example 2
The difference from example 1 is that copper nitrate in step (1) was replaced with iron nitrate.
Comparative example 3
The difference from example 1 is that the stearic acid particles in step (2) are replaced with perfluorooctanoic acid.
Performance testing
The hydrophobic antibacterial and antifungal materials provided in examples 1 to 4 and comparative examples 1 to 3 were subjected to a performance test by the following method:
(1) specific surface area: carrying out vacuum degassing pretreatment for 12h at 50 ℃ to remove impurities adsorbed on the surface of the sample, then testing, and selecting adsorption and desorption gas as nitrogen by adopting a BET method;
(2) antibacterial and mildewproof properties: the antibacterial performance of the sample is characterized according to the antibacterial loop method described in GB/T21510-2008.
The method comprises the following specific steps: dissolving 15.0g of nutrient agar in 500mL of normal saline to adjust the pH value to 7.0, sterilizing in an autoclave for 20min, subpackaging the nutrient agar on a culture medium after complete sterilization, cooling to solidify under natural conditions, then uniformly distributing 0.15mL of bacterial dispersion liquid cultured for 5 days at 37 ℃ on the culture medium, tabletting a sample to be tested (the diameter is 5.0mm) under aseptic conditions, placing the sample on the culture medium, culturing for 24h at 37 ℃, and representing the antibacterial capacity of the sample by the change of the diameter of a bacterial zone;
(3) hydrophobic property: the water contact angle of the sample was measured using a sessile drop contact angle/interfacial tensiometer.
The test results are shown in table 1:
TABLE 1
| Sample (I) | Specific surface area (m)2·g-1) | Antibacterial and antimildew (diameter of zone/mm) | Water contact Angle (°) |
| Example 1 | 524.35 | 10.0 | 150 |
| Example 2 | 502.17 | 9.8 | 140 |
| Example 3 | 511.20 | 9.9 | 142 |
| Example 4 | 501.72 | 9.8 | 145 |
| Comparative example 1 | 507.8 | 10.0 | Rapidly penetrate |
| Comparative example 2 | 505.13 | 5.0 | 140 |
| Comparative example 3 | 503.25 | 6.3 | 95 |
The embodiment and the performance test show that the hydrophobic antibacterial and mildewproof material provided by the invention has the characteristics of large specific surface area, good hydrophobicity and excellent antibacterial and mildewproof performance, wherein the specific surface area is 500m2·g-1Above, the diameter of the inhibition zone in the antibacterial and antifungal test is more than 9.5mm, and the water contact angle is more than 140 degrees.
From the comparison between example 1 and comparative example 1, it is understood that the addition of a hydrophobic agent such as stearic acid imparts an excellent hydrophobic effect to the material, and the water droplets are spherical, and the shape does not change with time, but the volume is decreasing; as can be seen from the comparison between example 1 and comparative example 2, the addition of the metal salt element having antibacterial properties imparts excellent antibacterial properties to the MOFs material. As can be seen from the comparison between example 1 and comparative example 3, the organic acid hydrophobizing agent is selected and mixed with the metal organic framework material, so that the hydrophobizing agent is dispersed more uniformly, and the hydrophobic effect is improved.
The applicant states that the invention is illustrated by the above examples to the hydrophobic antibacterial and antifungal material of the present invention and the preparation method and application thereof, but the invention is not limited to the above detailed method, i.e., it does not mean that the invention must be implemented by the above detailed method. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A hydrophobic antibacterial mildew-proof material is characterized by comprising a metal organic framework material and a hydrophobic agent dispersed in the metal organic framework material;
the metal organic framework material comprises any one or the combination of at least two of a copper-based metal organic framework material, a zinc-based metal organic framework material, a magnesium-based metal organic framework material or a silver-based metal organic framework material.
2. The hydrophobic, antibacterial, and antifungal material as claimed in claim 1 wherein the hydrophobic agent is selected from organic acid hydrophobic agents including any one or a combination of at least two of stearic acid, linoleic acid, linolenic acid, lauric acid, or oleic acid.
3. The hydrophobic antibacterial and mildewproof material as claimed in claim 1 or 2, wherein the mass ratio of the metal organic framework material to the hydrophobic agent is 100 (1-10).
4. The hydrophobic, antibacterial, and mildewproof material according to any one of claims 1 to 3, wherein the composition of the metal organic framework material comprises an organic ligand, and the organic ligand is an organic acid;
preferably, the organic acid is selected from phthalic acid and/or benzenetricarboxylic acid, and further preferably any one or a combination of at least two of 2, 5-dihydroxyterephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid or 2, 5-dinitro-1, 3, 4-benzenetricarboxylic acid.
5. The method for preparing a hydrophobic antimicrobial and mildewproofing material according to any one of claims 1 to 4, wherein the method comprises the steps of:
(1) mixing and crystallizing metal salt and organic ligand to obtain the metal organic framework material;
(2) and mixing the metal organic framework material with a hydrophobic agent, heating and drying to obtain the hydrophobic antibacterial mildewproof material.
6. The preparation method according to claim 5, wherein the mass ratio of the metal salt to the organic ligand is 1 (5-20);
preferably, the metal salt consists of a metal cation and an anion;
preferably, the metal cation is selected from any one or a combination of at least two of copper ion, zinc ion, magnesium ion or silver ion;
preferably, the anion comprises any one or a combination of at least two of sulfate, phosphate, chloride, iodide, sulfide or phosphate ions.
7. The production method according to claim 5 or 6, wherein the mixing of step (1) is carried out in a mixed solvent;
preferably, the mixed solvent comprises a combination of N, N-dimethylformamide, deionized water and absolute ethanol;
preferably, the volume ratio of the N, N-dimethylformamide to the deionized water to the absolute ethyl alcohol is (0.5-1): 1-2): 1;
preferably, the mixing of step (1) is carried out in ultrasound for a time of 15-90 min;
preferably, the crystallization temperature is 100-150 ℃, and the crystallization time is 5-20 h.
8. The method according to any one of claims 5 to 7, wherein the step (1) further comprises filtering, washing, drying after crystallization;
preferably, the washing comprises washing with N, N-dimethylformamide and then with anhydrous ethanol;
preferably, the drying temperature is 80-150 ℃ and the drying time is 6-12 h.
9. The production method according to any one of claims 5 to 8, wherein the mixing of step (2) is carried out in a solvent which is anhydrous ethanol;
preferably, the mixing in the step (2) is ultrasonic mixing for 10-40 min;
preferably, the heating temperature in the step (2) is 100-150 ℃, and the time is 1-5 h;
preferably, the drying temperature in the step (2) is 100-150 ℃, and the time is 1-5 h.
10. Use of a hydrophobic antimicrobial and mould resistant material according to any of claims 1-4 in an adsorbent, a catalyst or a hydrogen storage material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911304359.7A CN110973132A (en) | 2019-12-17 | 2019-12-17 | Hydrophobic antibacterial mildew-proof material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911304359.7A CN110973132A (en) | 2019-12-17 | 2019-12-17 | Hydrophobic antibacterial mildew-proof material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110973132A true CN110973132A (en) | 2020-04-10 |
Family
ID=70094872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911304359.7A Pending CN110973132A (en) | 2019-12-17 | 2019-12-17 | Hydrophobic antibacterial mildew-proof material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110973132A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113502165A (en) * | 2021-06-01 | 2021-10-15 | 中山大学 | Hydrophobic bulk material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336774A (en) * | 2011-07-20 | 2012-02-01 | 中国科学院化学研究所 | Method for synthesizing BTC (1,3,5-benzenetricarboxylic acid)-based nanoscale organometallic framework material |
| CN103756646A (en) * | 2014-02-11 | 2014-04-30 | 北京科技大学 | Preparation method of metal organic framework based composite phase-change material |
| CN103752239A (en) * | 2014-02-11 | 2014-04-30 | 北京科技大学 | Preparation method of metal organic framework coated phase-change material microcapsule |
| CN109384935A (en) * | 2017-08-08 | 2019-02-26 | 中国石油化工股份有限公司 | A kind of metal-organic framework materials and preparation method thereof |
-
2019
- 2019-12-17 CN CN201911304359.7A patent/CN110973132A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336774A (en) * | 2011-07-20 | 2012-02-01 | 中国科学院化学研究所 | Method for synthesizing BTC (1,3,5-benzenetricarboxylic acid)-based nanoscale organometallic framework material |
| CN103756646A (en) * | 2014-02-11 | 2014-04-30 | 北京科技大学 | Preparation method of metal organic framework based composite phase-change material |
| CN103752239A (en) * | 2014-02-11 | 2014-04-30 | 北京科技大学 | Preparation method of metal organic framework coated phase-change material microcapsule |
| CN109384935A (en) * | 2017-08-08 | 2019-02-26 | 中国石油化工股份有限公司 | A kind of metal-organic framework materials and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张四奇: ""固体储氢材料的研究综述"", 《材料研究与应用》 * |
| 张明龙等: "《企业管理出版社》", 31 May 2016 * |
| 林建好等: "《土木工程材料》", 31 August 2013, 哈尔滨工程大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113502165A (en) * | 2021-06-01 | 2021-10-15 | 中山大学 | Hydrophobic bulk material and preparation method thereof |
| CN113502165B (en) * | 2021-06-01 | 2022-05-20 | 中山大学 | Hydrophobic bulk material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108589266B (en) | Preparation method of nano metal particle/metal organic framework composite antibacterial cellulose fiber | |
| Zhao et al. | Uniform and stable immobilization of metal-organic frameworks into chitosan matrix for enhanced tetracycline removal from water | |
| Guo et al. | A chitosan-graphene oxide/ZIF foam with anti-biofouling ability for uranium recovery from seawater | |
| CN109400890A (en) | A kind of preparation method of multi-stage porous metal-organic framework materials | |
| KR20070092592A (en) | Adsorbent for water adsorption and desorption | |
| CN109880470B (en) | Preparation method of water-based acrylate time-delay antibacterial coating | |
| KR20190100803A (en) | Manufacturing method of porous metal-organic frameworks with heterogeneous pores using decarboxylation | |
| CN107793309B (en) | Metal organic framework material HKUST-1 and preparation method thereof | |
| CN110252267B (en) | Preparation and application of nano hybrid material | |
| CN107573344A (en) | A kind of preparation method and applications of biological metal organic frame complex | |
| CN111450806A (en) | Preparation method of porous adsorption antibacterial composite material based on waste corncobs | |
| CN111346609A (en) | Adsorbing material for heavy metal dye-containing wastewater and preparation method thereof | |
| US10829592B2 (en) | Method for preparing polyaniline complex with antimicrobial activity and heavy metal removal efficiency using conductive poly aniline polymer doped with organic acid and metal ion in defined order | |
| CN111676695A (en) | Dual-antibacterial non-woven fabric and preparation method thereof | |
| CN111013545A (en) | Preparation method and application of magnetic covalent organic framework | |
| CN114277576B (en) | Preparation method of multifunctional cotton fabric loaded with Cu-MOFs | |
| CN110973132A (en) | Hydrophobic antibacterial mildew-proof material and preparation method and application thereof | |
| CN115045113A (en) | Silver-loaded antibacterial fabric and preparation method and application thereof | |
| Zhang et al. | In situ generated UiO-66/cotton fabric easily recyclable for reactive dye adsorption | |
| CN108314868B (en) | Lignin composite hydrogel and preparation method thereof | |
| CN109876774B (en) | Adsorption material for treating dye sewage and preparation method thereof | |
| CN111957299B (en) | Functionalized copper-based MOFs material and preparation method and application thereof | |
| CN111269431B (en) | Preparation method of ZIF-67 nanoflower | |
| CN116732783A (en) | Metal organic framework composite antibacterial film and preparation method thereof | |
| CN111635537A (en) | Metal-organic framework material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210805 Address after: 224001 group 1, village committee of the people's Federation of China, Tinghu New District, Yancheng City, Jiangsu Province (28) Applicant after: JIANGSU ZHONGKE RUISAI POLLUTION CONTROL ENGINEERING Co.,Ltd. Applicant after: Institute of Process Engineering, Chinese Academy of Sciences Address before: 224001 group 1, village committee of the people's Federation of China, Tinghu New District, Yancheng City, Jiangsu Province (28) Applicant before: JIANGSU ZHONGKE RUISAI POLLUTION CONTROL ENGINEERING Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200410 |
|
| RJ01 | Rejection of invention patent application after publication |