CN107858046A - A kind of super-hydrophobic coat with automatically cleaning and antibacterial functions and preparation method thereof - Google Patents
A kind of super-hydrophobic coat with automatically cleaning and antibacterial functions and preparation method thereof Download PDFInfo
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- CN107858046A CN107858046A CN201711045125.6A CN201711045125A CN107858046A CN 107858046 A CN107858046 A CN 107858046A CN 201711045125 A CN201711045125 A CN 201711045125A CN 107858046 A CN107858046 A CN 107858046A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
Abstract
The invention belongs to super-hydrophobic coat preparing technical field, and in particular to a kind of super-hydrophobic coat with automatically cleaning and antibacterial functions and preparation method thereof.PVDF solid suspension A are prepared using the organic solution and small-molecular-weight alcohol of Kynoar, ZIF nano particles are then added in suspending liquid A, the fluoride for adding low-surface-energy afterwards obtains super-hydrophobic coat solution；By super-hydrophobic coat solution coated in substrate, the super-hydrophobic coat with automatically cleaning and antibacterial functions is prepared.The invention provides a kind of super-hydrophobic coat with automatically cleaning and antibacterial functions, preparation technology is simple, and reaction condition is gentle, is applicable to a variety of different substrates and large-scale production, and heat endurance and chemical stability are good.Super-hydrophobic coat not only has self-cleaning function to surface contaminant, while can also kill the bacterium of coating surface, prevents the formation of biomembrane, has great potential using value in automatically cleaning and antibacterial field.
Description
Technical field
The invention belongs to super-hydrophobic coat preparing technical field, and in particular to a kind of super with automatically cleaning and antibacterial functions
Hydrophobic coating and preparation method thereof.
Background technology
The research of biomimetic super hydrophobic surface is a frontier in chemical simulation biosystem research.Moved in nature
It is very universal that plant reaches the phenomenon of self-cleaning function by forming super hydrophobic surface, such as lotus leaf, plumage, water skipper leg
And butterfly's wing etc..Wherein most typical example is exactly lotus leaf surface of the mud without dye, has extremely strong automatically cleaning energy
Power, it is referred to as lotus leaf effect (lotus effect) by people.Lotus leaf surface is made up of many mastoid processes, and the average diameter of mastoid process is
5~9 μm.Water contact angle on a surface and roll angle are respectively 161.0 ± 2.7 ° and 2 °.Each mastoid process is by average diameter
Formed for 124.3 ± 3.2nm nanostructured branch.Nanostructured is equally existed in the lower layer of surface of lotus leaf, it can have
Effect ground prevents the lower floor of lotus leaf wetted.The supramastoid nanostructured of these nanostructureds, especially micron, super-hydrophobicity is risen
To important effect, self-cleaning feature is total to by the mastoid process of micro nano structure on rough surface and the presence of surface wax
With caused.The super-hydrophobic phenomenon of lotus leaf surface provides practical basis to prepare biomimetic super hydrophobic surface.Bionic super-hydrophobic
Surfacing has special micro and nano structure, therefore shows a series of excellent properties such as automatically cleaning, anti-pollution.
In the natures such as lotus leaf, water skipper leg, butterfly's wing under the inspiration of super-hydrophobicity tissue and organ, bionic super-hydrophobic
The target of design and the research and development of surfacing is not only in that the functional structure of mimic biology, and more important is prepare component and structure
Adjustable super hydrophobic surface, so as to obtain existing hydrophobic self-cleaning property, while the performance such as intensity, heat-resisting, acid and alkali-resistance is again very
Excellent new material.Such material has broad application prospects in national defence, industry, agricultural, medical science and daily life.
The wetability of the surface of solids is together decided on by its chemical composition and micro-geometry.It is well known that wettability
Mainly influenceed by chemistry of solid surfaces composition, Solid Surface Free Energy is bigger, easier to be soaked by some liquid, on the contrary
It is as the same.The preparation of super hydrophobic surface often need to cover fluorocarbon chain or silane chain to reduce surface energy on surface.But in smooth surface
Glazing adjusts surface free energy using chemical method, be generally only capable of making contact angle increase to 120 ° and can not be high again.Reach
The surface fine structure of more high contact angle, just necessary designing material, the surface with fine coarse structure (are relatively shorter than drop
Micro-meter scale) will can effectively improve thin (parent) water surface dredge (parent) water-based energy.
Kynoar is a kind of new thermoplastic fluorocarbon resin, has excellent processing characteristics, mechanical strength, heat steady
Qualitative and excellent chemical stability, and its surface energy is relatively low, therefore it is widely used as super hydrophobic material.Super hydrophobic surface
The adhesion of liquid and solid particle can be prevented, but easily by the organic matter and microorganism pollution in water.Many researchs all concentrate on
On the self-cleaning performance on these surfaces, the research of antibiotic property but have ignored.Therefore, self-cleaning function and antibacterial functions are provided simultaneously with
Super-hydrophobic coat more have use value.
The content of the invention
It is an object of the invention to provide a kind of super-hydrophobic coat with automatically cleaning and antibacterial functions and preparation method thereof.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of preparation method of the super-hydrophobic coat with automatically cleaning and antibacterial functions, utilizes the organic molten of Kynoar
Liquid and small-molecular-weight alcohol prepare PVDF solid suspension A, and ZIF nano particles are then added in suspending liquid A, are added afterwards low
The fluoride of surface energy obtains super-hydrophobic coat solution；By super-hydrophobic coat solution coated in substrate, prepare with certainly
Cleaning and the super-hydrophobic coat of antibacterial functions.
Wherein, the mass concentration of the organic solution of the Kynoar is 2~5%, and the mass ratio with small component alcohol is
1:9；The amount that ZIF nano particles add is the 0.3~1.0% of suspending liquid A quality, and the addition of low-surface-energy fluoride is suspension
The 0.5~1.5% of liquid A mass.
The solvent of the organic solution of Kynoar is preferably DMAC N,N' dimethyl acetamide, N,N-dimethylformamide or N-
Any one in methyl pyrrolidone.
Described small-molecular-weight alcohol is preferably methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol, propane diols, glycerine, butanol
Or any one in amylalcohol.
Described ZIF nano particles preferably select any one in ZIF-8, ZIF-67 and ZIF-7.
The preparation of ZIF nano particles is preferably but not limited to be carried out as follows：, will be organic by dissolving metal salts in the solvents of X 1
Part is dissolved in the solvents of X 2, and both are mixed, and ZIF particle suspension liquids are made, and is made through centrifuging, washing, drying and grinding
Obtain ZIF nano particles.
The fluoride of the low-surface-energy is preferably 17 fluorine decyl trimethoxy silanes, 17 fluorine decyl triethoxysilicanes
Alkane, ten trifluoro octyl group trimethoxy silanes, tridecafluoro-n-octyltriethoxysilane, ten difluoro heptyl propyl trimethoxy silicanes,
Any one in nine fluorine hexyl trimethoxy silanes, nine fluorine hexyl triethoxysilanes, pentafluorophenyl group triethoxysilane.
Described substrate is preferably in non-woven fabrics, cotton, filter paper, nylon cloth, commercial polypropylene nitrile film or polystyrene film
Any one.
Specifically, the preparation process of super-hydrophobic coat solution is as follows：Kynoar (PVDF) solution is added drop-wise to small point
In son amount alcohol, 10~20min is sufficiently mixed, 20~40min is then ultrasonically treated and prepares micron-sized PVDF solid suspensions A；
Then ZIF nano particles are added in suspending liquid A, are sufficiently mixed 10~20min, are then ultrasonically treated 30~60min；Finally plus
Enter the fluoride of low-surface-energy, super-hydrophobic coat solution is obtained after stirring 10-12h.
During by super-hydrophobic coat solution coated in substrate, it can use any one in dipping, spin coating, spraying and drop coating
Kind.
The substrate treated by super-hydrophobic coat solution can be evaporated by 50~100 DEG C of heating, can also be dried in the air naturally
It is dry.
Specifically, a kind of preparation method of the super-hydrophobic coat with automatically cleaning and antibacterial functions of the present invention, including it is following
Step：
(1) preparation of ZIF nano particles：By dissolving metal salts in solvent X1, organic ligand is dissolved in X2 solvents,
Both are mixed, ZIF particle suspension liquids can be made, ZIF powder is made through centrifuging, washing, drying and grinding；
(2) preparation of super-hydrophobic coat solution：Kynoar (PVDF) solution that mass fraction is 2~5% is added dropwise
Into small-molecular-weight alcohol, the mass ratio of PVDF solution and small-molecular-weight alcohol is 1:9.It is then super by being stirred vigorously 10~20min
20~40min of sonication, micron-sized PVDF solid suspensions are prepared with this；Then mass fraction is added in suspension is
0.3~1.0% ZIF nano particles, 10~20min is stirred vigorously, is ultrasonically treated 30~60min, is eventually adding mass fraction
For 0.5~1.5% fluoride with low-surface-energy, after magnetic agitation 12h, super-hydrophobic coat solution is obtained；
(3) preparation of super-hydrophobic coat：By coating solution by deposition technique coated in substrate, by heating evaporation or
Naturally the method volatilized can prepare the super-hydrophobic coat with automatically cleaning and antibacterial functions.
In numerous anti-biotic materials, zeolite imidazole skeleton (ZIF) is a kind of important porous material of organic and inorganic mixed crystallization
Material, have surface area big, crystallinity is high, and pore volume is big, aperture size is adjustable, thermostabilization and the advantages that chemically stable.It is prepared
Method has been prior art, is no longer described in detail herein.
, in the solution can be with metastable because ZIF nano-particles have excellent heat endurance and chemical stability
In the presence of, and metal ion and organic ligand with antibacterial action are slowly gradually discharged, continue so as to reach long-term
The purpose of antibacterial.The present invention prepares super-hydrophobic coat based on ZIF nano particles, and surface has micron and nanometer composite structure, by 2 microlitres
Water droplet is added in coating surface, and its contact angle is 159~166 °, and roll angle is less than 5 ° because high static contact angle and compared with
Small roll angle assigns super-hydrophobic coat excellent automatical cleaning ability.In addition, relative to the Ag particles that are widely used and
TiO2Particle, ZIF nano particles have fabulous antibacterial effect, and production cost is relatively low, can be real under normal temperature condition
Existing antibacterial functions, it is not necessary to the additional conditions such as ultraviolet.As a kind of new multi-functional super-hydrophobic coat, be expected in automatically cleaning and
Antibacterial field obtains extensive use, and the bacteriostasis rate of the coating can reach 100% substantially.
In the preparation process of super-hydrophobic coat, the solution of Kynoar (PVDF), which is added in small-molecular-weight alcohol, is
The process of inversion of phases is carried out, is ultrasonically treated afterwards to prepare PVDF colloidal suspension particles.Then ZIF is added in system to receive
Rice grain, PVDF/ZIF-8 composite colloid suspended particulates are prepared by ultrasound and stir process, then after the modification of perfluoro-compound
Super-hydrophobic antibacterial be can be prepared by solution.The coating solution can by the methods of drop coating, dip-coating and spraying coated on different
In substrate.Obtained coating surface has fabulous super not only with coarse micro-nano structure and with relatively low surface energy
Hydrophobic property, and show excellent self-cleaning function and antibacterial functions.
The present invention compared with prior art, has the following advantages that：
The preparation technology of super-hydrophobic coat of the present invention with automatically cleaning and antibacterial functions is simple, and reaction condition is gentle, can
Suitable for a variety of different substrates and large-scale production, heat endurance and chemical stability are good.Super-hydrophobic coat is not only to surface
Pollutant has self-cleaning function, while can also kill the bacterium of coating surface, prevents the formation of biomembrane, in automatically cleaning and
Antibacterial field has great potential using value.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph on super-hydrophobic coat surface in embodiment 1；
Fig. 2 is the atomic force microscopy diagram on super-hydrophobic coat surface in embodiment 1；
Fig. 3 is the still photo that water droplet is dropped in the substrate for scribbling super-hydrophobic coat solution in embodiment 1, and substrate is respectively
(a) PAN films, (b) fabric, (c) filter paper, (d) non-woven fabrics；
Fig. 4 is that water droplet is dropped in the PAN film substrates with super-hydrophobic coat sprinkled with active carbon powder in embodiment 1；
Fig. 5 is that water droplet is dropped in the blank substrate sprinkled with active carbon powder in embodiment 1；
Fig. 6 is the antibacterial effect figure of antibacterial experiment blank control in embodiment 1；
Fig. 7 is the antibacterial effect figure of super-hydrophobic coat in embodiment 1.
Embodiment
Technical scheme, but protection scope of the present invention not limited to this are illustrated with specific embodiment below：
Embodiment 1
A kind of super-hydrophobic coat with automatically cleaning and antibacterial functions, preparation method are as follows：
1) ZIF-8 nano particles are synthesized using triethylamine as guiding agent in aqueous：Take 0.733g Zn (NO3)2·
6H2O is dissolved in 100mL deionized water, then take 3.244g 2-methylimidazole (Hmim) and 4g triethylamines (TEA) be dissolved in it is another
In part 100mL deionized water, at room temperature, zinc nitrate aqueous solution is rapidly added in Hmim the and TEA solution that stirred and continued
Stir 10min.Then 8000rpm centrifuges 10min and collects precipitation and be washed with deionized, in triplicate.By the ZIF-8 of acquisition
Nano particle is dried in vacuo 24h at 40 DEG C, then grinds standby.
2) super-hydrophobic coat solution is prepared：First, 3g PVDF are added in 97g DMAs and stir 2h
To form PVDF clear solution.Secondly, take 10g PVDF solution to be mixed with 90g ethanol, be stirred vigorously 20min, then will be mixed
Compound is ultrasonically treated 30min and obtains PVDF solid suspension.0.5g ZIF-8 nano particles are dispersed in above-mentioned system and surpassed
Sound 10min, finally, 1.0g tridecafluoro-n-octyltriethoxysilanes are added in said mixture, after magnetic agitation 12h, obtained
To super-hydrophobic coat solution；
3) super-hydrophobic coat is prepared：Using polyacrylonitrile business milipore filter PAN as model substrates substrate, PAN films are fixed on
In component, the area that film surface can be coated by solution is 28.26cm2.By the method for drop coating by 1mL super-hydrophobic coat solution
Drip on film surface, then film is put into baking oven 1h is dried at 50 DEG C with evaporation solvent, in order to eliminate super-hydrophobic coat
Surface defect, repetitive coatings once, again dry 1h with evaporation solvent at 50 DEG C.Thus it is made and is based on ZIF-8 nano particles
Super-hydrophobic coat with automatically cleaning and antibacterial functions.
Super-hydrophobic coat solution can be also coated on the surface of filter paper, non-woven fabrics or textile, and following examples are identical.
Super-hydrophobic coat self-cleaning function detects：
By above-mentioned steps 3) the formation PAN films that have super-hydrophobic coat after the processing of super-hydrophobic coat solution are attached to flat board
On, flat board is then tilted 10 ° or so, active carbon powder is sprinkling upon coating surface.Water is slowly added dropwise from film surface, observes
The automatically cleaning effect of coating.60000 times of observation samples are amplified using field emission scanning electron microscope (FESEM, FEI, Quanta250FEG)
The microscopic appearance on product surface, as shown in figure 1, coating surface is common due to micron order PVDF particles and nanoscale ZIF-8 particles
Effect successfully constructs micro-nano structure.Seen with AFM (AFM, Bruker Dimension Fastscan, USA)
Surface roughness is examined, as shown in Fig. 2 super-hydrophobic coat surface profile root-mean-square-deviation Rq=207nm, it was demonstrated that coating surface has
Larger roughness.
Using the contact angle on the prepared super-hydrophobic coat surface of contact angle measurement measure, as shown in figure 3, by super thin
The polyacrylonitrile business milipore filter of water process, filter paper, the water droplet contact angle of non-woven fabrics and textile are up to 159~166 °, and it is rolled
Dynamic 5 ° of the equal little Yu in angle.Due to there is preferable self-cleaning function with higher contact angle and less roll angle, coating, such as scheme
Shown in 4, water droplet is easy to quickly roll off from surface so as to take away the pollutant on surface.And undressed counterdie does not have then
Self-cleaning function, as shown in figure 5, water droplet can adhere to substrate surface.
The antibacterial activity detection of super-hydrophobic coat：
Escherichia coli stoste (200uL) is added to the test tube containing sterile Luria-Bertani (LB) meat soup (10mL)
In, then cultivate 4h in 37 DEG C, 170rpm incubators.Each sample (coating that blank test group and step 3) obtain) takes
10cm2Size is cut into strip and immerses E. coli broth (100uL) and sterile saline solution (10mL) containing culture
Test tube in, at 37 DEG C, under 170rpm be incubated 2h after, the suspension system is suctioned out into 0.5ml from test tube, then with sterile salt
The aqueous solution prepares a series of ten times of dilutions.Solution coating after finally 100uL is diluted is on agar medium and in 37 DEG C of trainings
12h is supported, each sample bacterium bacterium colony is counted.Each sample carries out three groups of antibacterial experiments simultaneously, using average value as experiment
As a result.It is as follows that Bacteria suppression rate calculates publicity：
Wherein R is bacteriostasis rate, and M, N are the clump count in blank control group and experiment study group culture medium respectively.Blank pair
According to the surface colony situation of group, as shown in fig. 6, there are a large amount of bacterium colonies in media surface.And super-hydrophobic coat fungistatic effect such as Fig. 7
Shown, media surface clump count is 0, and its bacteriostasis rate reaches 100%.
Embodiment 2
A kind of super-hydrophobic coat with automatically cleaning and antibacterial functions, preparation method are as follows：
1) ZIF-8 nano particles are synthesized using triethylamine as guiding agent in aqueous：With embodiment 1；
2) super-hydrophobic coat solution is prepared：First, 3g PVDF are added in 97g DMFs and stir 2h
To form PVDF clear solution.Secondly, 10g PVDF solution is mixed with 90g ethanol, is stirred vigorously 20min, then will be mixed
Compound is ultrasonically treated 30min and obtains PVDF solid suspension.0.5g ZIF-8 nano particles are dispersed in above-mentioned system and surpassed
Sound 10min, finally, 1.0g tridecafluoro-n-octyltriethoxysilanes are added in said mixture, after magnetic agitation 12h, obtained
To super-hydrophobic coat solution；
3) super-hydrophobic coat is prepared：Using PAN films as substrate (similarly hereinafter), other are the same as embodiment 1.
Method according to embodiment 1 carries out the detection of super-hydrophobic coat self-cleaning function and the antibacterial activity of super-hydrophobic coat is examined
Survey, its contact angle is 163 °, and roll angle is 3 °；Bacteriostasis rate is 100%.
Embodiment 3
A kind of super-hydrophobic coat with automatically cleaning and antibacterial functions, preparation method are as follows：
1) ZIF-8 nano particles are synthesized using triethylamine as guiding agent in aqueous：By the ZIF-8 nano particles of acquisition
24h is dried in vacuo at 50 DEG C, then grinds standby, other are the same as embodiment 1.
2) super-hydrophobic coat solution is prepared：First, by 3g PVDF be added in 97g 1-METHYLPYRROLIDONEs stir 2h with
Form PVDF clear solution.Secondly, 10g PVDF solution is mixed with 90g ethanol, is stirred vigorously 30min, then will mixing
Thing is ultrasonically treated 30min and obtains PVDF solid suspension.0.5g ZIF-8 nano particles are dispersed in above-mentioned system ultrasonic
10min, finally, 1.0g tridecafluoro-n-octyltriethoxysilanes are added in said mixture, after magnetic agitation 12h, obtained
Super-hydrophobic coat solution；
3) super-hydrophobic coat is prepared：With embodiment 1.
Method according to embodiment 1 carries out the detection of super-hydrophobic coat self-cleaning function and the antibacterial activity of super-hydrophobic coat is examined
Survey, its contact angle is 165 °, and roll angle is 2 °；Bacteriostasis rate is 100%.
Embodiment 4
A kind of super-hydrophobic coat with automatically cleaning and antibacterial functions, preparation method are as follows：
1) ZIF-8 nano particles are synthesized using triethylamine as guiding agent in aqueous：With embodiment 1；
2) super-hydrophobic coat solution is prepared：First, 3g PVDF are added in 97g DMAs and stir 2h
To form PVDF clear solution.Secondly, 10g PVDF solution is mixed with 90g methanol, is stirred vigorously 20min, then will be mixed
Compound is ultrasonically treated 30min and obtains PVDF solid suspension.0.5g ZIF-8 nano particles are dispersed in above-mentioned system and surpassed
Sound 10min, finally, 1.0g tridecafluoro-n-octyltriethoxysilanes are added in said mixture, after magnetic agitation 12h, obtained
To super-hydrophobic coat solution；
3) super-hydrophobic coat is prepared：With embodiment 1.
Method according to embodiment 1 carries out the detection of super-hydrophobic coat self-cleaning function and the antibacterial activity of super-hydrophobic coat is examined
Survey, its contact angle is 164 °, and roll angle is 2 °；Bacteriostasis rate is 100%.
Embodiment 5
A kind of super-hydrophobic coat with automatically cleaning and antibacterial functions, preparation method are as follows：
1) ZIF-8 nano particles are synthesized in methanol solution：Take 1.465g Zn (NO3)2·6H2O is dissolved in 100mL first
In alcohol, then 3.245g 2-methylimidazole (Hmim) is taken to be dissolved in another 100mL methanol, it is then, zinc nitrate/methanol is molten
Liquid is rapidly added in the Hmim/ methanol solutions that stirred, and the change of solution slowly is muddy, continues to centrifuge after reacting 1h at room temperature,
Precipitation is taken, is washed after three times to be put into 50 DEG C of vacuum drying chamber with methanol solution and dried, grinding is stand-by；
2) super-hydrophobic coat solution is prepared：First, 3g PVDF are added in 97g DMAs and stir 2h
To form PVDF clear solution.Secondly, 10g PVDF solution is mixed with 90g methanol, is stirred vigorously 20min, then will be mixed
Compound is ultrasonically treated 30min and obtains PVDF solid suspension.0.5g ZIF-8 nano particles are dispersed in above-mentioned system and surpassed
Sound 10min, finally, 1.0g tridecafluoro-n-octyltriethoxysilanes are added in said mixture, after magnetic agitation 12h, obtained
To super-hydrophobic coat solution；
3) super-hydrophobic coat is prepared：With embodiment 1.
Method according to embodiment 1 carries out the detection of super-hydrophobic coat self-cleaning function and the antibacterial activity of super-hydrophobic coat is examined
Survey, its contact angle is 162 °, and roll angle is 4 °；Bacteriostasis rate is 100%.
Embodiment 6
A kind of super-hydrophobic coat with automatically cleaning and antibacterial functions, preparation method are as follows：
1) ZIF-67 nano particles are prepared：Take 1.8g Co (NO3)2·6H2O is dissolved in 12mL deionized waters, 22g 2-
Methylimidazole is dissolved in 80mL deionized waters.That is n (Co (NO3)2·6H2O):N (2-methylimidazole):N (water)=1:58.Will
Two solution are mixed, and 6h is stirred under normal temperature, are then centrifuged for collecting ZIF-67 solids and are washed with deionized 3 times.It will finally be made
Be deposited in 80 DEG C under the conditions of be dried in vacuo 24h, obtain ZIF-67 nano particles.
2) super-hydrophobic coat solution is prepared：First, 3g PVDF are added in 97g DMAs and stir 2h
To form PVDF clear solution.Secondly, 10g PVDF solution is mixed with 90g methanol, is stirred vigorously 20min, then will be mixed
Compound is ultrasonically treated 30min and obtains PVDF solid suspension.0.4g ZIF-67 nano particles are dispersed in above-mentioned system and surpassed
Sound 10min, finally, 1.0g tridecafluoro-n-octyltriethoxysilanes are added in said mixture, after magnetic agitation 12h, obtained
To super-hydrophobic coat solution；
3) super-hydrophobic coat is prepared：With embodiment 1.
Method according to embodiment 1 carries out the detection of super-hydrophobic coat self-cleaning function and the antibacterial activity of super-hydrophobic coat is examined
Survey, its contact angle is 166 °, and roll angle is 3 °；Bacteriostasis rate is 100%.
Embodiment 7
A kind of super-hydrophobic coat with automatically cleaning and antibacterial functions, preparation method are as follows：
1) ZIF-7 nano particles are prepared：By 0.453g Zn (NO3)2·6H2O and 1.154g benzimidazoles are added to 150mL
In DMF, 23h is stirred at room temperature.Then product is centrifuged and washed three times with methanol.Because N,
Dinethylformamide is relatively difficult to remove, so be stirred for 24h in methyl alcohol by the precipitation of acquisition is scattered, is then centrifuged for point
From being dried in vacuo 24h under the conditions of being deposited in 50 DEG C, obtain ZIF-7 nano particles；
2) super-hydrophobic coat solution is prepared：First, 3g PVDF are added in 97g DMAC and stir 2h to form PVDF's
Clear solution.Secondly, 10g PVDF solution is mixed with 90g methanol, 20min is stirred vigorously, is then ultrasonically treated mixture
30min obtains PVDF solid suspension.0.5gZIF-7 nano particles are dispersed in ultrasonic 10min in above-mentioned system, finally,
1.0g tridecafluoro-n-octyltriethoxysilanes are added in said mixture, after magnetic agitation 12h, it is molten to obtain super-hydrophobic coat
Liquid；
3) super-hydrophobic coat is prepared：With embodiment 1.
Method according to embodiment 1 carries out the detection of super-hydrophobic coat self-cleaning function and the antibacterial activity of super-hydrophobic coat is examined
Survey, its contact angle is 163 °, and roll angle is 5 °；Bacteriostasis rate is 100%.
Claims (10)
1. a kind of preparation method of the super-hydrophobic coat with automatically cleaning and antibacterial functions, it is characterised in that utilize polyvinylidene fluoride
The organic solution and small-molecular-weight alcohol of alkene prepare PVDF solid suspension A, and ZIF nano particles are then added in suspending liquid A, it
The fluoride for adding low-surface-energy afterwards obtains super-hydrophobic coat solution；By super-hydrophobic coat solution coated in substrate, prepare
Obtain the super-hydrophobic coat with automatically cleaning and antibacterial functions.
2. the preparation method of the super-hydrophobic coat as claimed in claim 1 with automatically cleaning and antibacterial functions, it is characterised in that
The mass concentration of the organic solution of the Kynoar is 2-5%, and the mass ratio with small component alcohol is 1:9；ZIF nano particles
The amount of addition is the 0.3~1.0% of suspending liquid A quality, the addition of low-surface-energy fluoride for suspending liquid A quality 0.5~
1.5%.
3. the preparation method of the super-hydrophobic coat as claimed in claim 1 with automatically cleaning and antibacterial functions, it is characterised in that
Described small-molecular-weight alcohol is appointing in methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol, propane diols, glycerine, butanol or amylalcohol
Meaning is a kind of.
4. the preparation method of the super-hydrophobic coat as claimed in claim 1 with automatically cleaning and antibacterial functions, it is characterised in that
Described ZIF nano particles select any one in ZIF-8, ZIF-67 and ZIF-7.
5. the preparation method of the super-hydrophobic coat as claimed in claim 1 with automatically cleaning and antibacterial functions, it is characterised in that
The fluoride of the low-surface-energy is that 17 fluorine decyl trimethoxy silanes, 17 fluorine decyl triethoxysilanes, ten trifluoros are pungent
Base trimethoxy silane, tridecafluoro-n-octyltriethoxysilane, ten difluoro heptyl propyl trimethoxy silicanes, nine fluorine hexyl front threes
Any one in TMOS, nine fluorine hexyl triethoxysilanes, pentafluorophenyl group triethoxysilane.
6. the preparation method of the super-hydrophobic coat as claimed in claim 1 with automatically cleaning and antibacterial functions, it is characterised in that
The solvent of the organic solution of Kynoar is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide or 1-METHYLPYRROLIDONE
In any one.
7. there is the preparation method of the super-hydrophobic coat of automatically cleaning and antibacterial functions as claimed in claim 1, it is characterised in that institute
The substrate stated is any one in non-woven fabrics, cotton, filter paper, nylon cloth, commercial polypropylene nitrile film or polystyrene film.
8. the preparation method of the super-hydrophobic coat with automatically cleaning and antibacterial functions as described in claim 1-7 is any, it is special
Sign is that the preparation process of super-hydrophobic coat solution is as follows：Kynoar (PVDF) solution is added drop-wise in small-molecular-weight alcohol,
10~20min is sufficiently mixed, 20~40min is then ultrasonically treated and prepares micron-sized PVDF solid suspensions A；Then suspending
ZIF nano particles are added in liquid A, are sufficiently mixed 10~20min, are then ultrasonically treated 30~60min；It is eventually adding low-surface-energy
Fluoride, stir 10-12h after obtain super-hydrophobic coat solution.
9. the preparation method of the super-hydrophobic coat as claimed in claim 8 with automatically cleaning and antibacterial functions, it is characterised in that
Preparing for ZIF nano particles is as follows：By dissolving metal salts in X1 solvents, organic ligand is dissolved in X2 solvents, incite somebody to action both
Mix, ZIF particle suspension liquids are made, ZIF nano particles are made through centrifuging, washing, drying and grinding.
10. the super-hydrophobic coat with automatically cleaning and antibacterial functions that claim 1-9 either method prepares.
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