CN104888623B - A kind of super hydrophilic composite porous film of Kynoar and its preparation method carrying silver-colored super hydrophilic film - Google Patents
A kind of super hydrophilic composite porous film of Kynoar and its preparation method carrying silver-colored super hydrophilic film Download PDFInfo
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- CN104888623B CN104888623B CN201510305804.7A CN201510305804A CN104888623B CN 104888623 B CN104888623 B CN 104888623B CN 201510305804 A CN201510305804 A CN 201510305804A CN 104888623 B CN104888623 B CN 104888623B
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Abstract
The preparation method that the present invention discloses a kind of super hydrophilic composite porous film of Kynoar and its carries silver-colored super hydrophilic film.The present invention is using the method for blending and inversion of phases film forming, and utilize the rough surface forming micro/nano level between phase-separable material and material of main part during inversion of phases, then membrane material is immersed in the solution containing DOPA compound and carries out surface modification, feature using the oxidation of DOPA compound, autohemagglutination, crosslinking, adhesion prepares super hydrophilic film to modifying surface, week reduction further with poly- DOPA or poly-dopamine reduces to silver ion, finally passes through the super hydrophilic film surface of the reaction preparation load silver of DOPA compound again.The ultra-hydrophilic surface being formed using the method and its ultra-hydrophilic surface of load silver have lasting super hydrophilicity and antibiotic property.
Description
Technical field
The present invention relates to separation membrane surface modification field, the super hydrophilic composite porous film of more particularly, to a kind of Kynoar and
It carries the preparation method of silver-colored super hydrophilic film.
Background technology
The surface with Superhydrophilic can give material unique performance, have important application, widely closed
Note and research.Ultra-hydrophilic surface is typically obtained by constructing the rough surface of the micro-nano-scale with certain hydrophilicity,
Wherein with nano-TiO2Based on the ultra-hydrophilic surface of construction.The ultra-hydrophilic surface preparation method of report is a lot, such as patent
CN201010120791.3 discloses a kind of super-hydrophilicity multifunctional coating surface and preparation method, the coating surface in the method
The oxide covering being made up of ionic oxide formation method is the surface of metal particles that forms of copper and copper alloy of substrate and electro-plating method preparation
Compound composition；Patent CN200910043839.2 discloses a kind of self-cleaning super-hydrophilic thin film and preparation method thereof, the method
With tetrabutyl titanate as TiO2Predecessor is prepared for rear-earth-doped TiO2Colloidal sol, and impregnated-lifting and roasting obtain thering is super parent
The surface of aqueouss energy；Patent CN02113348.4 discloses a kind of titanium dioxide and tin ash photocatalysis Superhydrophilic THIN COMPOSITE
Film, prepares titanium dioxide and tin ash complex sol, impregnated-lifting and high-temperature roasting method system using sol-gel process
For the surface with super hydrophilicity；Macromolecular Rapid Communications 26 (2005) 87-92 reports
Road carries out, in material surface, the surface that reverse micro emulsion UV surface photografting is prepared for having super hydrophilicity；Journal of
Colloid and Interface Science 316 (2007) 206 209 reports Nano-meter SiO_22Mix with polystyrene
It is prepared for the surface with super hydrophilicity by controlling baking temperature.
Kynoar (PVDF) is one of more extensive membrane material of current application, and it has good chemically stable
Property, heat stability and higher mechanical strength.But because its stronger hydrophobicity easily causes fouling membrane, give it in water treatment applications
In bring certain problem.Pvdf membrane material is carried out with hydrophilic modifying is very necessary.Research report in terms of hydrophilic modifying
Road is a lot, but the research that it is carried out with super hydrophilic modification is fewer.Patent CN201010222482.7 discloses a kind of super close
The manufacture method of water type ultrafilter membrane and equipment, the super hydrophilicity in this patent is to pvdf membrane surface by Ethanol Plasma
Carry out obtained from alcoholization process, cost of equipment is high；Patent CN200710173870.9 discloses in a kind of membrane bioreactor
The method of modifying of membrane material, by nano-TiO in the method2Dispersion liquid is sprayed on pvdf membrane outer surface thus reaching super hydrophilic
Property.Due to being weaker adsorption, nano-TiO2Application process is easy to come off, makes the super hydrophilicity of film unstable
Fixed, the nano-TiO simultaneously coming off2Also can environment be caused potentially threaten；Patent ZL 201110127998.8 is by polyvinylidene fluoride
The mixing such as alkene, the copolymer containing maleic anhydride, solvent and aperture adjustment agent, with ethanol for coagulating bath after inversion of phases molding, then
Film is immersed in and after soaking in the solution of amino silane, obtains super hydrophilic polyvinylidene fluoride film.The method preparation time is long, needs 4
～6 days and can only using the copolymer containing maleic anhydride and it needs to anhydride is carried out certain protection ensure its activity.Super close
Moisture film preparation efficiency is relatively low, and process conditions require relatively stringent.
Content of the invention
The purpose of the present invention is for the deficiencies in the prior art, provides a kind of super hydrophilic composite porous film of Kynoar
Preparation method.
For reaching above-mentioned purpose, the step that the present invention adopts is as follows：
Step (1), Kynoar, split-phase polymer, aperture adjustment agent, solvent are carried out dissolving mix homogeneously, vacuum
Preparation liquid is obtained after deaeration；Preparation liquid is become after liquid film entrance coagulating bath by scraper or extrusion die, through solution inversion of phases and
The compound porous counterdie of Kynoar is obtained after cleaning；Weight/mass percentage composition in preparation liquid for wherein each raw material is as follows：5～
20 Kynoar, 2～8 split-phase polymer, 1～5 aperture adjustment agent, 67～92 solvents；
Described split-phase polymer is polrvinyl chloride, chliorinated polyvinyl chloride, polrvinyl chloride/- vinyl acetate co-polymer, poly-
One or more of styrene, polystyrene/copolymer-maleic anhydride, polysulfones, polyether sulfone, polyacrylonitrile；
Described solvent be DMF, N,N-dimethylacetamide, trimethyl phosphate, triethyl phosphate,
One or more of dimethyl sulfoxide, N-Methyl pyrrolidone mixed liquor；
Described aperture adjustment agent is one or more of Polyvinylpyrrolidone, Polyethylene Glycol, glycerol, diethylene glycol；
Step (2), the compound porous counterdie of Kynoar of preparation in step (1) is immersed in the water of DOPA compound
Soak reaction 24 hours in solution, after taking out cleaning-drying, obtain the described super hydrophilic composite porous film of Kynoar；Wherein
In DOPA compound water solution, the mass percentage concentration of DOPA compound is 0.05～0.3；
Described DOPA compound is 3,4 dihydroxy benzenes alanines (DOPA) or 4- (2- ethylamino-) benzene -1,2- glycol
(dopamine).
Another object of the present invention is for the deficiencies in the prior art, provides a kind of Kynoar to carry silver-colored super hydrophilic film
Preparation method.
Step (1), Kynoar, split-phase polymer, aperture adjustment agent, solvent are carried out dissolving mix homogeneously, vacuum
Preparation liquid is obtained after deaeration；Preparation liquid is become after liquid film entrance coagulating bath by scraper or extrusion die, through solution inversion of phases and
The compound porous counterdie of Kynoar is obtained after cleaning；Weight/mass percentage composition in preparation liquid for wherein each raw material is as follows：5～
20 Kynoar, 2～8 split-phase polymer, 1～5 aperture adjustment agent, 67～92 solvents；
Described split-phase polymer is polrvinyl chloride, chliorinated polyvinyl chloride, polrvinyl chloride/- vinyl acetate co-polymer, poly-
One or more of styrene, polystyrene/copolymer-maleic anhydride, polysulfones, polyether sulfone, polyacrylonitrile；
Described solvent be DMF, N,N-dimethylacetamide, trimethyl phosphate, triethyl phosphate,
One or more of dimethyl sulfoxide, N-Methyl pyrrolidone mixed liquor；
Described aperture adjustment agent is one or more of Polyvinylpyrrolidone, Polyethylene Glycol, glycerol, diethylene glycol；
Step (2), the compound porous counterdie of Kynoar of preparation in step (1) is immersed in the water of DOPA compound
Soak reaction 24 hours in solution, after taking out cleaning-drying, obtain the described super hydrophilic composite porous film of Kynoar；Wherein
In DOPA compound water solution, the mass percentage concentration of DOPA compound is 0.05～0.3；
Described DOPA compound is 3,4 dihydroxy benzenes alanines (DOPA) or 4- (2- ethylamino-) benzene -1,2- glycol
(dopamine)；
Step (3), the super hydrophilic composite porous film of Kynoar obtaining in step (2) is immersed in silver ammino solution instead
Add reducing agent after answering 0.5～6 hour, be further continued for reacting 4～12 hours, after taking out cleaning, obtain the polyvinylidene fluoride that surface carries silver
Alkene composite porous film, the Kynoar composite porous film that surface is carried silver is immersed in the aqueous solution of DOPA compound again
Soak reaction 24 hours, after taking out cleaning-drying, obtain the described super hydrophilic film of load silver；Wherein reducing agent consumption is silver ammino solution
1.5～3 times of middle silver nitrate quality；
Described reducing agent is glucose, Polyvinylpyrrolidone, sodium ascorbate, vitamin C, citric acid or citric acid
Sodium.
The beneficial effects of the present invention is：
The present invention using the method for blending and inversion of phases film forming, and using between phase-separable material and material of main part during inversion of phases
Form the rough surface of micro/nano level, then membrane material is immersed in the solution containing DOPA compound and carries out surface and change
Property, the feature using the oxidation of DOPA compound, autohemagglutination, crosslinking, adhesion is prepared super hydrophilic film, is entered one to modifying surface
Step is reduced to silver ion using the week reduction of poly- DOPA or poly-dopamine, finally passes through the reaction of DOPA compound again
The super hydrophilic film surface of preparation load silver.The ultra-hydrophilic surface being formed using the method and its ultra-hydrophilic surface of load silver are had
Persistently super hydrophilicity and antibiotic property.
Brief description
Fig. 1 is the Kynoar compound porous counterdie electron microscopic picture of embodiment 1-3 preparation.
Fig. 2 is the Kynoar super hydrophilic composite porous film electron microscopic picture of embodiment 1-3 preparation.
Specific embodiment
With reference to specific embodiment, the present invention is further analyzed, comprises the following steps that：
(1) Kynoar being 5%～20% by mass percent, mass percent is 2%～8% split-phase polymerization
Thing, mass percent be 1%～5% aperture adjustment agent and solvent that mass percent is 67%～92% carry out dissolving mixing
Uniformly, obtain preparation liquid after vacuum defoamation；Preparation liquid is become entrance coagulating bath after liquid film by scraper or extrusion die, through solution
The compound porous counterdie of Kynoar is obtained after inversion of phases and cleaning.
(2) the compound porous counterdie of Kynoar of preparation in step (1) is immersed in the aqueous solution of DOPA compound
Middle immersion is reacted 24 hours, obtains the described super hydrophilic composite porous film of Kynoar, wherein DOPA after taking out cleaning-drying
In class compound water solution, the mass percentage concentration of DOPA compound is 0.05～0.3.
(3) the super hydrophilic composite porous film of Kynoar obtaining in step (2) is immersed in silver ammino solution and reacts 0.5
Add reducing agent after～6 hours, be further continued for reacting 4～12 hours, the Kynoar obtaining surface load silver after taking out cleaning is multiple
Close perforated membrane, the Kynoar composite porous film that surface is carried silver is again immersed in the aqueous solution of DOPA compound and soaks
Reaction 24 hours, obtains the described super hydrophilic film of load silver, wherein, reducing agent consumption is silver nitrate quality after taking out cleaning-drying
1.5～3 times.
Described split-phase polymer is polrvinyl chloride, chliorinated polyvinyl chloride, and polrvinyl chloride/- vinyl acetate co-polymer gathers
Styrene, polystyrene/copolymer-maleic anhydride, polysulfones, polyether sulfone, one or more of polyacrylonitrile mixes.Described
Solvent is DMF, N,N-dimethylacetamide, trimethyl phosphate, triethyl phosphate, dimethyl sulfoxide, N- first
One of base ketopyrrolidine or any mixed liquor.Described aperture adjustment agent is Polyvinylpyrrolidone, Polyethylene Glycol, sweet
One or more of oil, diethylene glycol.Described DOPA compound is 3,4 dihydroxy benzenes alanines (DOPA), 4- (2- ethamine
Base) benzene -1,2- glycol (dopamine).Described reducing agent is glucose, Polyvinylpyrrolidone, sodium ascorbate, vitamin
C, citric acid, sodium citrate.
According to the preparation method of a kind of above-mentioned compound aromatic micro-capsule and its load silver aromatic micro-capsule, below with specifically real
Apply example and describe the present invention in detail.The implementation steps of all embodiments are identical with abovementioned steps.It should be noted that described embodiment
It is not construed as limiting the invention, those of ordinary skill in the art can directly derive from present disclosure or associate
All deformation, be all considered as protection scope of the present invention.
Prepare compound aromatic micro-capsule first, see specific embodiment：
Embodiment 1-1.
(1) quality is respectively the Kynoar of 5g, the split-phase polymer poly vinyl chloride of 2g, the aperture adjustment agent of 1g gathers
The solvent DMF of ethylene glycol and 92g carries out dissolving mix homogeneously, obtains preparation liquid after vacuum defoamation；By masking
Liquid enters coagulating bath after scraper becomes liquid film, obtains the compound porous counterdie of Kynoar after solution inversion of phases and cleaning.
(2) the compound porous counterdie of Kynoar of preparation in step (1) being immersed in mass percentage concentration is more than 0.3
Soak reaction 24 hours in bar compound water solution, obtain described Kynoar after taking out cleaning-drying super hydrophilic compound many
Pore membrane.
20 DEG C of the film surface water static contact angle of embodiment 1-1 preparation is less than 10 °, complete wetting in 1s.
Embodiment 1-2.
(1) quality is respectively the Kynoar of 20g, the split-phase polymer poly ether sulfone of 1g, the split-phase polymer poly of 3g
Phenylethylene/maleic anhydride copolymer, the aperture adjustment agent diethylene glycol of 5g and the solvent N,N-dimethylacetamide of 71g are dissolved
Mix homogeneously, obtains preparation liquid after vacuum defoamation；Preparation liquid is become entrance coagulating bath after liquid film by extrusion die, through solution
The compound porous counterdie of Kynoar is obtained after conversion and cleaning.
(2) the compound porous counterdie of Kynoar of preparation in step (1) being immersed in mass percentage concentration is more than 0.2
Soak reaction 24 hours in bar amine compound aqueous solution, obtain described Kynoar after taking out cleaning-drying super hydrophilic compound
Perforated membrane.
20 DEG C of the film surface water static contact angle of embodiment 1-2 preparation is less than 10 °, complete wetting in 1s.
Embodiment 1-3.
(1) quality is respectively the Kynoar of 10g, the split-phase polymer polysulfones of 2g, the split-phase polymer polyphenyl of 6g
Ethylene, the aperture adjustment agent Polyvinylpyrrolidone of 1g, the aperture adjustment agent Polyethylene Glycol of 3g and the solvent N of 50g, N- dimethyl
Acetamide, the solvent triethyl phosphate of 28g carries out dissolving mix homogeneously, obtains preparation liquid after vacuum defoamation；Preparation liquid is passed through
Scraper enters coagulating bath after becoming liquid film, obtains the compound porous counterdie of Kynoar after solution inversion of phases and cleaning.
(2) the compound porous counterdie of Kynoar of preparation in step (1) being immersed in mass percentage concentration is 0.15
Soak reaction 24 hours in DOPA amine compound aqueous solution, obtain described Kynoar after taking out cleaning-drying super hydrophilic multiple
Close perforated membrane.
20 DEG C of the film surface water static contact angle of embodiment 1-3 preparation is less than 10 °, complete wetting in 1s.As shown in Figure 1 may be used
Substantially to see the split-phase microsphere that Kynoar compound porous counterdie surface has the formation of split-phase polymer, many as shown in Figure 2
There is significant change in bottom hole film microsphere surface after poly-dopamine modified lithium.
Embodiment 1-4.
(1) quality is respectively the Kynoar of 15g, the split-phase polymer chliorinated polyvinyl chloride of 1g, the split-phase of 5g is gathered
Compound polrvinyl chloride/- vinyl acetate co-polymer, the aperture adjustment agent glycerol of 1g, the aperture adjustment agent Polyethylene Glycol of 2g and 50g
Solvent DMF, the solvent trimethyl phosphate of 26g carries out dissolving mix homogeneously, obtains masking after vacuum defoamation
Liquid；Preparation liquid is become entrance coagulating bath after liquid film by extrusion die, after solution inversion of phases and cleaning, obtains Kynoar
Compound porous counterdie.
(2) the compound porous counterdie of Kynoar of preparation in step (1) being immersed in mass percentage concentration is 0.05
Soak reaction 24 hours in DOPA compound water solution, obtain described Kynoar after taking out cleaning-drying super hydrophilic compound
Perforated membrane.
20 DEG C of the film surface water static contact angle of embodiment 1-4 preparation is less than 10 °, complete wetting in 1s.
Embodiment 1-5.
(1) quality is respectively the Kynoar of 8g, the split-phase polymer poly acrylonitrile of 1g, the split-phase polymer poly of 2g
Phenylethylene/maleic anhydride copolymer, the aperture adjustment agent Polyethylene Glycol of 2g and the solvent N,N-dimethylacetamide of 60g, 27g's
Solvent dimethyl sulfoxide carries out dissolving mix homogeneously, obtains preparation liquid after vacuum defoamation；Preparation liquid is become after liquid film by scraper
Enter coagulating bath, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar.
(2) the compound porous counterdie of Kynoar of preparation in step (1) being immersed in mass percentage concentration is 0.25
Soak reaction 24 hours in DOPA compound water solution, obtain described Kynoar after taking out cleaning-drying super hydrophilic compound
Perforated membrane.
20 DEG C of the film surface water static contact angle of embodiment 1-5 preparation is less than 10 °, complete wetting in 1s.
Embodiment 1-6.
(1) quality is respectively the Kynoar of 13g, the split-phase polymer poly ether sulfone of 2g, the split-phase polymer poly of 3g
Vinyl chloride/- vinyl acetate co-polymer, the aperture adjustment agent diethylene glycol of 3g, 1g aperture adjustment agent Polyethylene Glycol, the solvent of 70g
N,N-dimethylacetamide, the solvent N-methyl pyrilidone of 8g carries out dissolving mix homogeneously, obtains preparation liquid after vacuum defoamation；
Preparation liquid is become entrance coagulating bath after liquid film by extrusion die, obtains Kynoar after solution inversion of phases and cleaning and be combined
Porous counterdie.
(2) the compound porous counterdie of Kynoar of preparation in step (1) being immersed in mass percentage concentration is more than 0.1
Soak reaction 24 hours in bar amine compound aqueous solution, obtain described Kynoar after taking out cleaning-drying super hydrophilic compound
Perforated membrane.
20 DEG C of the film surface water static contact angle of embodiment 1-6 preparation is less than 10 °, complete wetting in 1s.
Embodiment 1-7
(1) quality is respectively the Kynoar of 20g, the split-phase polymer chliorinated polyvinyl chloride of 8g, the aperture of 5g is adjusted
The solvent DMF of section agent Polyvinylpyrrolidone and 67g carries out dissolving mix homogeneously, obtains after vacuum defoamation
Preparation liquid；Preparation liquid is become entrance coagulating bath after liquid film by scraper, after solution inversion of phases and cleaning, obtains Kynoar
Compound porous counterdie.
(2) the compound porous counterdie of Kynoar of preparation in step (1) being immersed in mass percentage concentration is more than 0.1
Soak reaction 24 hours in bar compound water solution, obtain described Kynoar after taking out cleaning-drying super hydrophilic compound many
Pore membrane.
20 DEG C of the film surface water static contact angle of embodiment 1-7 preparation is less than 10 °, complete wetting in 1s.
Embodiment 1-8
Embodiment 1-7 experiment condition split-phase polymer chliorinated polyvinyl chloride is replaced with polrvinyl chloride/- vinylacetate common
Polymers, solvent DMF replaces with triethyl phosphate, and aperture adjustment agent Polyvinylpyrrolidone replaces with glycerol,
Other experiment conditions are constant, finally prepare the super hydrophilic composite porous film of Kynoar.The film surface of embodiment 1-8 preparation
20 DEG C of water static contact angles are less than 10 °, complete wetting in 1s.
Embodiment 1-9
Embodiment 1-7 experiment condition split-phase polymer chliorinated polyvinyl chloride is replaced with polystyrene, solvent N, N- diformazan
Base Methanamide replaces with dimethyl sulfoxide, and aperture adjustment agent Polyvinylpyrrolidone replaces with diethylene glycol, and other experiment conditions are not
Become, finally prepare the super hydrophilic composite porous film of Kynoar.20 DEG C of the film surface water Static Contact of embodiment 1-9 preparation
Angle is less than 10 °, complete wetting in 1s.
Embodiment 1-10
Embodiment 1-7 experiment condition split-phase polymer chliorinated polyvinyl chloride is replaced with polystyrene/maleic anhydride
Thing, solvent DMF replaces with N-Methyl pyrrolidone, and other experiment conditions are constant, finally prepares poly- inclined
The super hydrophilic composite porous film of fluorothene.20 DEG C of the film surface water static contact angle of embodiment 1-10 preparation is less than 10 °, in 1s completely
Moistening.
Embodiment 1-11
Embodiment 1-7 experiment condition split-phase polymer chliorinated polyvinyl chloride is replaced with polysulfones, other experiment conditions are constant,
Finally prepare the super hydrophilic composite porous film of Kynoar.20 DEG C of the film surface water static contact angle of embodiment 1-11 preparation
Less than 10 °, complete wetting in 1s.
Embodiment 1-12
Embodiment 1-7 experiment condition split-phase polymer chliorinated polyvinyl chloride is replaced with polyether sulfone, other experiment conditions are not
Become, finally prepare the super hydrophilic composite porous film of Kynoar.20 DEG C of the film surface water static state of embodiment 1-12 preparation connects
Feeler is less than 10 °, complete wetting in 1s.
Embodiment 1-13
Embodiment 1-7 experiment condition split-phase polymer chliorinated polyvinyl chloride is replaced with polyacrylonitrile, other experiment conditions
Constant, finally prepare the super hydrophilic composite porous film of Kynoar.20 DEG C of the film surface water static state of embodiment 1-13 preparation
Contact angle is less than 10 °, complete wetting in 1s.
Then carried using the super hydrophilic compound porous film preparation Kynoar of the Kynoar obtaining in above-described embodiment
The super hydrophilic film of silver, is shown in specific embodiment：
Embodiment 2-1.
Super hydrophilic for the Kynoar preparing to above-described embodiment 1-1 composite porous film is cut into 5cm × 5cm size
After be immersed in 100g silver ammino solution reaction 0.5 hour after add 3g reducing agent glucose, be further continued for reacting 4 hours, take out clear
The Kynoar composite porous film that surface carries silver is obtained, the Kynoar composite porous film that surface is carried silver soaks again after washing
Enter in the aqueous solution of DOPA compound and soak reaction 24 hours, after taking out cleaning-drying, obtain the described super hydrophilic film of load silver,
Wherein, in silver ammino solution, silver nitrate mass concentration is 2, and reducing agent consumption is 1.5 times of silver nitrate quality.
20 DEG C of the film surface water static contact angle of embodiment 2-1 preparation is less than 10 °, and complete wetting in 1s, to escherichia coli
Sterilizing rate is 99.9%.
Embodiment 2-2.
Super hydrophilic for the Kynoar preparing to above-described embodiment 1-2 composite porous film is cut into 5cm × 5cm size
After be immersed in 100g silver ammino solution reaction 1 hour after add 6g reducing agent Polyvinylpyrrolidone, be further continued for reacting 12 hours,
Obtain the Kynoar composite porous film that surface carries silver after taking out cleaning, surface is carried the Kynoar composite porous film of silver
Again it is immersed in the aqueous solution that weight/mass percentage composition is 0.2 DOPA amines and soaks reaction 24 hours, take out cleaning dry
The described super hydrophilic film of load silver is obtained, wherein, in silver ammino solution, silver nitrate mass concentration is 2, and reducing agent consumption is nitre after dry
3 times of the silver amount of acid.
20 DEG C of the film surface water static contact angle of embodiment 2-2 preparation is less than 10 °, and complete wetting in 1s, to escherichia coli
Sterilizing rate is 99.8%.
Embodiment 2-3.
Super hydrophilic for the Kynoar preparing to above-described embodiment 1-3 composite porous film is cut into 5cm × 5cm size
After be immersed in 100g silver ammino solution reaction 2 hours after add 4g reducing agent vitamin C, be further continued for reacting 6 hours, take out cleaning
Obtain the Kynoar composite porous film that surface carries silver afterwards, the Kynoar composite porous film that surface is carried silver immerses again
Soak reaction 24 hours in the aqueous solution being 0.15 DOPA amines to weight/mass percentage composition, obtain after taking out cleaning-drying
The described super hydrophilic film of load silver, wherein, in silver ammino solution, silver nitrate mass concentration is 2, and reducing agent consumption is silver nitrate quality
2 times.
20 DEG C of the film surface water static contact angle of embodiment 2-3 preparation is less than 10 °, and complete wetting in 1s, to escherichia coli
Sterilizing rate is 99.9%.
Embodiment 2-4.
Super hydrophilic for the Kynoar preparing to above-described embodiment 1-4 composite porous film is cut into 5cm × 5cm size
After be immersed in 100g silver ammino solution reaction 5 hours after add 5g reducing agent sodium ascorbate, be further continued for reacting 8 hours, take out
Obtain the Kynoar composite porous film that surface carries silver after cleaning, surface is carried silver-colored Kynoar composite porous film again
It is immersed in the aqueous solution that weight/mass percentage composition is 0.05 DOPA compound and soaks reaction 24 hours, obtain after taking out cleaning-drying
To the described super hydrophilic film of load silver, wherein, in silver ammino solution, silver nitrate mass concentration is 2, and reducing agent consumption is that nitric acid is silver
2.5 times of amount.
20 DEG C of the film surface water static contact angle of embodiment 2-4 preparation is less than 10 °, and complete wetting in 1s, to escherichia coli
Sterilizing rate is 99.8%.
Embodiment 2-5.
Super hydrophilic for the Kynoar preparing to above-described embodiment 1-5 composite porous film is cut into 5cm × 5cm size
After be immersed in 100g silver ammino solution reaction 3 hours after add 3g reducing agent citric acid, be further continued for reacting 10 hours, take out cleaning
Obtain the Kynoar composite porous film that surface carries silver afterwards, the Kynoar composite porous film that surface is carried silver immerses again
Soak reaction 24 hours in the aqueous solution being 0.25 DOPA compound to weight/mass percentage composition, after taking out cleaning-drying, obtain institute
The super hydrophilic film of load silver stated, wherein, in silver ammino solution, silver nitrate mass concentration is 2, and reducing agent consumption is silver nitrate quality
1.5 again.
20 DEG C of the film surface water static contact angle of embodiment 2-5 preparation is less than 10 °, and complete wetting in 1s, to escherichia coli
Sterilizing rate is 99.7%.
Embodiment 2-6.
Super hydrophilic for the Kynoar preparing to above-described embodiment 1-6 composite porous film is cut into 5cm × 5cm size
After be immersed in 100g silver ammino solution reaction 2.5 hours after add 4g reducing agent sodium citrate, be further continued for reacting 10 hours, take out
Obtain the Kynoar composite porous film that surface carries silver after cleaning, surface is carried silver-colored Kynoar composite porous film again
It is immersed in the aqueous solution that weight/mass percentage composition is 0.1 DOPA amines and soaks reaction 24 hours, after taking out cleaning-drying
Obtain the described super hydrophilic film of load silver, wherein, in silver ammino solution, silver nitrate mass concentration is 2, and reducing agent consumption is silver nitrate
2 times of quality.
20 DEG C of the film surface water static contact angle of embodiment 2-6 preparation is less than 10 °, and complete wetting in 1s, to escherichia coli
Sterilizing rate is 99.9%.
Embodiment 2-7.
Super hydrophilic for the Kynoar preparing to above-described embodiment 1-7 composite porous film is cut into 5cm × 5cm size
After be immersed in 100g silver ammino solution reaction 6 hours after add 5g reducing agent Polyvinylpyrrolidone, be further continued for reacting 12 hours,
Obtain the Kynoar composite porous film that surface carries silver after taking out cleaning, surface is carried the Kynoar composite porous film of silver
Again it is immersed in the aqueous solution that weight/mass percentage composition is 0.1 DOPA compound and soaks reaction 24 hours, take out cleaning-drying
Obtain the described super hydrophilic film of load silver afterwards, wherein, in silver ammino solution, silver nitrate mass concentration is 2, and reducing agent consumption is nitric acid
2.5 times of silver amount.
20 DEG C of the film surface water static contact angle of embodiment 2-7 preparation is less than 10 °, and complete wetting in 1s, to escherichia coli
Sterilizing rate is 99.9%.
Embodiment 2-8.
The super hydrophilic composite porous film of Kynoar that embodiment 1-7 in embodiment 2-7 is prepared is substituted for enforcement
The super hydrophilic composite porous film of Kynoar that example 1-8 prepares, other experiment conditions are constant, finally obtain load silver super hydrophilic
Film.20 DEG C of the film surface water static contact angle of embodiment 2-8 preparation is less than 10 °, and complete wetting in 1s, to escherichia coli sterilizing rate
For 99.9%.
Embodiment 2-9.
The super hydrophilic composite porous film of Kynoar that embodiment 1-7 in embodiment 2-7 is prepared is substituted for enforcement
The super hydrophilic composite porous film of Kynoar that example 1-9 prepares, other experiment conditions are constant, finally obtain load silver super hydrophilic
Film.20 DEG C of the film surface water static contact angle of embodiment 2-9 preparation is less than 10 °, and complete wetting in 1s, to escherichia coli sterilizing rate
For 99.9%.
Embodiment 2-10.
The super hydrophilic composite porous film of Kynoar that embodiment 1-7 in embodiment 2-7 is prepared is substituted for enforcement
The super hydrophilic composite porous film of Kynoar that example 1-10 prepares, other experiment conditions are constant, finally obtain load silver super close
Moisture film.20 DEG C of the film surface water static contact angle of embodiment 2-10 preparation is less than 10 °, and complete wetting in 1s is killed to escherichia coli
Bacterium rate is 99.9%.
Embodiment 2-11.
The super hydrophilic composite porous film of Kynoar that embodiment 1-7 in embodiment 2-7 is prepared is substituted for enforcement
The super hydrophilic composite porous film of Kynoar that example 1-11 prepares, other experiment conditions are constant, finally obtain load silver super close
Moisture film.20 DEG C of the film surface water static contact angle of embodiment 2-11 preparation is less than 10 °, and complete wetting in 1s is killed to escherichia coli
Bacterium rate is 99.9%.
Embodiment 2-12.
The super hydrophilic composite porous film of Kynoar that embodiment 1-7 in embodiment 2-7 is prepared is substituted for enforcement
The super hydrophilic composite porous film of Kynoar that example 1-12 prepares, other experiment conditions are constant, finally obtain load silver super close
Moisture film.20 DEG C of the film surface water static contact angle of embodiment 2-12 preparation is less than 10 °, and complete wetting in 1s is killed to escherichia coli
Bacterium rate is 99.9%.
Embodiment 2-13.
The super hydrophilic composite porous film of Kynoar that embodiment 1-7 in embodiment 2-7 is prepared is substituted for enforcement
The super hydrophilic composite porous film of Kynoar that example 1-13 prepares, other experiment conditions are constant, finally obtain load silver super close
Moisture film.20 DEG C of the film surface water static contact angle of embodiment 2-13 preparation is less than 10 °, and complete wetting in 1s is killed to escherichia coli
Bacterium rate is 99.9%.
Above-described embodiment is not the restriction for the present invention, and the present invention is not limited only to above-described embodiment, as long as meeting
Application claims, belong to protection scope of the present invention.
Claims (6)
1. a kind of Kynoar carries the preparation method of silver-colored super hydrophilic film it is characterised in that the method comprises the following steps：
Step (1), Kynoar, split-phase polymer, aperture adjustment agent, solvent are carried out dissolving mix homogeneously, vacuum defoamation
After obtain preparation liquid；Preparation liquid is become entrance coagulating bath after liquid film by scraper or extrusion die, through solution inversion of phases and cleaning
After obtain the compound porous counterdie of Kynoar；Weight/mass percentage composition in preparation liquid for wherein each raw material is as follows：5～20 gather
Vinylidene, 2～8 split-phase polymer, 1～5 aperture adjustment agent, 67～92 solvents；
Split-phase polymer described in step (1) be polrvinyl chloride, chliorinated polyvinyl chloride, polrvinyl chloride/- vinyl acetate copolymerized
One or more of thing, polystyrene, polysulfones, polyether sulfone, polyacrylonitrile；
Described aperture adjustment agent is one or more of Polyethylene Glycol, glycerol, diethylene glycol；
Step (2), the compound porous counterdie of Kynoar of preparation in step (1) is immersed in the aqueous solution of DOPA compound
Middle immersion is reacted 24 hours, obtains the described super hydrophilic composite porous film of Kynoar after taking out cleaning-drying；
Step (3), the super hydrophilic composite porous film of Kynoar obtaining in step (2) is immersed in silver ammino solution reaction
Add reducing agent after 0.5～6 hour, be further continued for reacting 4～12 hours, after taking out cleaning, obtain the Kynoar that surface carries silver
Composite porous film, the Kynoar composite porous film that surface is carried silver is again immersed in the aqueous solution of DOPA compound and soaks
Bubble reaction 24 hours, obtains the described super hydrophilic film of load silver after taking out cleaning-drying.
2. a kind of Kynoar carries the preparation method of silver-colored super hydrophilic film it is characterised in that step (1) as claimed in claim 1
Described solvent is DMF, N,N-dimethylacetamide, trimethyl phosphate, triethyl phosphate, dimethyl are sub-
One or more of sulfone, N-Methyl pyrrolidone mixed liquor.
3. a kind of Kynoar carries the preparation method of silver-colored super hydrophilic film it is characterised in that step (2) as claimed in claim 1
Described DOPA compound is 3,4 dihydroxy benzenes alanines or 4- (2- ethylamino-) benzene -1,2- glycol.
4. a kind of Kynoar carries the preparation method of silver-colored super hydrophilic film it is characterised in that step (2) as claimed in claim 1
In DOPA compound water solution, the mass percentage concentration of DOPA compound is 0.05～0.3.
5. a kind of Kynoar carries the preparation method of silver-colored super hydrophilic film it is characterised in that step (3) as claimed in claim 1
Described reducing agent is glucose, Polyvinylpyrrolidone, sodium ascorbate, vitamin C, citric acid or sodium citrate.
6. a kind of Kynoar carries the preparation method of silver-colored super hydrophilic film it is characterised in that step (3) as claimed in claim 1
Reducing agent consumption is 1.5～3 times of silver nitrate quality in silver ammino solution.
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| CN114225709B (en) * | 2021-12-14 | 2024-03-26 | 浙江工业大学 | Preparation method of super-amphiphilic oil-water separation film for fixing in-situ grown silver nano particles |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102240510A (en) * | 2011-05-18 | 2011-11-16 | 浙江大学 | Method for preparing super-hydrophilic polyvinylidene fluoride membrane |
| CN103394295A (en) * | 2013-08-14 | 2013-11-20 | 哈尔滨工业大学 | Hydrophilic PVDF (Polyvinylidene Fluoride) composite ultrafiltration membrane and preparation method thereof |
| CN103418250A (en) * | 2013-07-05 | 2013-12-04 | 烟台绿水赋膜材料有限公司 | Method of in-situ generation of nano particle on separating membrane surface |
| CN103464013A (en) * | 2013-07-25 | 2013-12-25 | 烟台绿水赋膜材料有限公司 | High-performance hybrid separation membrane and preparation method thereof |
| CN103613780A (en) * | 2013-11-14 | 2014-03-05 | 中国科学院化学研究所 | Method for surface modification of hydrophobic polymer microporous membrane |
| CN104275099A (en) * | 2014-10-30 | 2015-01-14 | 哈尔滨工业大学 | Preparation method of underwater super-oleophobic modified polyvinylidene fluoride membrane |
-
2015
- 2015-06-04 CN CN201510305804.7A patent/CN104888623B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102240510A (en) * | 2011-05-18 | 2011-11-16 | 浙江大学 | Method for preparing super-hydrophilic polyvinylidene fluoride membrane |
| CN103418250A (en) * | 2013-07-05 | 2013-12-04 | 烟台绿水赋膜材料有限公司 | Method of in-situ generation of nano particle on separating membrane surface |
| CN103464013A (en) * | 2013-07-25 | 2013-12-25 | 烟台绿水赋膜材料有限公司 | High-performance hybrid separation membrane and preparation method thereof |
| CN103394295A (en) * | 2013-08-14 | 2013-11-20 | 哈尔滨工业大学 | Hydrophilic PVDF (Polyvinylidene Fluoride) composite ultrafiltration membrane and preparation method thereof |
| CN103613780A (en) * | 2013-11-14 | 2014-03-05 | 中国科学院化学研究所 | Method for surface modification of hydrophobic polymer microporous membrane |
| CN104275099A (en) * | 2014-10-30 | 2015-01-14 | 哈尔滨工业大学 | Preparation method of underwater super-oleophobic modified polyvinylidene fluoride membrane |
Non-Patent Citations (1)
| Title |
|---|
| 材料表面仿生修饰及金属化的研究;廖园;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20110115(第01期);第23-24页 * |
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