CN104888623A - Polyvinylidene fluoride super-hydrophilic composite porous membrane and preparation method of silver-loaded super-hydrophilic membrane thereof - Google Patents
Polyvinylidene fluoride super-hydrophilic composite porous membrane and preparation method of silver-loaded super-hydrophilic membrane thereof Download PDFInfo
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- CN104888623A CN104888623A CN201510305804.7A CN201510305804A CN104888623A CN 104888623 A CN104888623 A CN 104888623A CN 201510305804 A CN201510305804 A CN 201510305804A CN 104888623 A CN104888623 A CN 104888623A
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Abstract
The invention discloses a polyvinylidene fluoride super-hydrophilic composite porous membrane and a preparation method of a silver-loaded super-hydrophilic membrane thereof. A blending method and a phase to membrane conversion method are adopted, a micro-nano-level rough surface is formed while the phase conversion is performed between a phase-splitting material and a main material, then the membrane material is soaked in a solution containing dopa compounds to perform surface modification, the surface is modified through the adoption of features of oxidation, auto-agglutination, crosslinking and adhesion of the dopa compounds to prepare the super-hydrophilic membrane, the weak reducibility of polydopa or polydopamine is further used for reducing silver ions, and finally the silver-loaded super-hydrophilic membrane surface is prepared through the reaction of the dopa compounds. The super-hydrophilic surface formed by the method and the silver-loaded super-hydrophilic surface thereof have durable super-hydrophilic performance and antibacterial property.
Description
Technical field
The present invention relates to separation membrane surface modification field, particularly relate to the preparation method of the super hydrophilic composite porous film of a kind of Kynoar and year super hydrophilic film of silver thereof.
Background technology
The performance of material uniqueness can be given in the surface with Superhydrophilic, has important application, is paid close attention to widely and study.Ultra-hydrophilic surface generally obtains, wherein with nano-TiO by there is the rough surface of the micro-nano-scale of certain hydrophilicity
2the ultra-hydrophilic surface of structure is main.The ultra-hydrophilic surface preparation method reported is a lot, as patent CN201010120791.3 discloses a kind of super-hydrophilicity multifunctional coating surface and preparation method, the oxide covering that the coating surface in the method is made up of ionic oxide formation method is that the surface of metal particles compound that copper and copper alloy prepared by substrate and electro-plating method forms forms; Patent CN200910043839.2 discloses a kind of self-cleaning super-hydrophilic thin film and preparation method thereof, and the method take tetrabutyl titanate as TiO
2predecessor has prepared rear-earth-doped TiO
2colloidal sol, and obtain the surface with super hydrophilicity through dipping-lift and roasting; Patent CN02113348.4 discloses a kind of titanium dioxide and tin ash photocatalysis Superhydrophilic laminated film, adopt sol-gel process to prepare titanium dioxide and tin ash complex sol, prepare the surface with super hydrophilicity through dipping-lift and high-temperature roasting method; Macromolecular Rapid Communications 26 (2005) 87-92 reports and carries out reverse micro emulsion UV surface photografting at material surface and prepared the surface with super hydrophilicity; Journal of Colloid and Interface Science 316 (2007) 206 – 209 reports Nano-meter SiO_2
2mix with polystyrene and prepared the surface with super hydrophilicity by controlling baking temperature.
Kynoar (PVDF) is current Application comparison one of membrane material widely, and it has good chemical stability, heat endurance and higher mechanical strength.But the hydrophobicity stronger due to it easily causes fouling membrane, in water treatment applications, bring certain problem to it.It is very necessary for carrying out hydrophilic modifying to pvdf membrane material.Research report in hydrophilic modifying is a lot, but fewer to its research carrying out super hydrophilic modifying.Patent CN201010222482.7 discloses a kind of preparation method and equipment of ultra-hydrophilic type ultrafiltration membrane, and the super hydrophilicity in this patent carries out alcoholization process by Ethanol Plasma to pvdf membrane surface and obtains, and cost of equipment is high; Patent CN200710173870.9 discloses the method for modifying of membrane material in a kind of membrane bioreactor, by nano-TiO in the method
2dispersion liquid is sprayed on pvdf membrane outer surface thus reaches Superhydrophilic.Owing to being more weak adsorption, nano-TiO
2be easy to come off in application process, make the super hydrophilicity of film unstable, the nano-TiO simultaneously come off
2also potential threat can be caused to environment; Patent ZL 201110127998.8 is by Kynoar, the copolymer containing maleic anhydride, the mixing such as solvent and aperture adjustment agent, with ethanol be coagulating bath after inversion of phases is shaping, then obtain super hydrophilic polyvinylidene fluoride membrane after soaking in solution film being immersed in amino silane.The method preparation time is long, needs 4 ~ 6 days and can only use the copolymer containing maleic anhydride, and needs to carry out certain protection to ensure that it is active to acid anhydrides.Super hydrophilic film preparation efficiency is lower, and process conditions require relatively strict.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, the preparation method of the super hydrophilic composite porous film of a kind of Kynoar is provided.
For achieving the above object, the step that the present invention adopts is as follows:
Step (1), Kynoar, phase-splitting polymer, aperture adjustment agent, solvent are carried out dissolving and mix, after vacuum defoamation, obtain preparation liquid; Enter coagulating bath after preparation liquid is become liquid film by scraper or extrusion die, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar; Wherein the mass percentage of each raw material in preparation liquid is as follows: 5 ~ 20 ﹪ Kynoar, 2 ~ 8 ﹪ phase-splitting polymer, 1 ~ 5 ﹪ aperture adjustment agent, 67 ~ 92 ﹪ solvents;
Described phase-splitting polymer is one or more in polyvinyl chloride, chliorinated polyvinyl chloride, polyvinyl chloride/-vinyl acetate co-polymer, polystyrene, polystyrene/copolymer-maleic anhydride, polysulfones, polyether sulfone, polyacrylonitrile;
Described solvent is one or more mixed liquors in DMF, DMA, trimethyl phosphate, triethyl phosphate, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE;
Described aperture adjustment agent is one or more in polyvinylpyrrolidone, polyethylene glycol, glycerine, diethylene glycol (DEG);
Step (2), the compound porous counterdie of Kynoar of preparation in step (1) is immersed in the aqueous solution of DOPA compound and soaks reaction 24 hours, after taking out cleaning-drying, obtain the super hydrophilic composite porous film of described 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 the preparation method of the super hydrophilic film of silver.
Step (1), Kynoar, phase-splitting polymer, aperture adjustment agent, solvent are carried out dissolving and mix, after vacuum defoamation, obtain preparation liquid; Enter coagulating bath after preparation liquid is become liquid film by scraper or extrusion die, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar; Wherein the mass percentage of each raw material in preparation liquid is as follows: 5 ~ 20 ﹪ Kynoar, 2 ~ 8 ﹪ phase-splitting polymer, 1 ~ 5 ﹪ aperture adjustment agent, 67 ~ 92 ﹪ solvents;
Described phase-splitting polymer is one or more in polyvinyl chloride, chliorinated polyvinyl chloride, polyvinyl chloride/-vinyl acetate co-polymer, polystyrene, polystyrene/copolymer-maleic anhydride, polysulfones, polyether sulfone, polyacrylonitrile;
Described solvent is one or more mixed liquors in DMF, DMA, trimethyl phosphate, triethyl phosphate, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE;
Described aperture adjustment agent is one or more in polyvinylpyrrolidone, polyethylene glycol, glycerine, diethylene glycol (DEG);
Step (2), the compound porous counterdie of Kynoar of preparation in step (1) is immersed in the aqueous solution of DOPA compound and soaks reaction 24 hours, after taking out cleaning-drying, obtain the super hydrophilic composite porous film of described 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), super for the Kynoar obtained hydrophilic composite porous film is immersed in silver ammino solution to react after 0.5 ~ 6 hour adds reducing agent in step (2), continue reaction again 4 ~ 12 hours, the Kynoar composite porous film that silver is carried on surface is obtained after taking out cleaning, Kynoar composite porous film surface being carried silver is again immersed in the aqueous solution of DOPA compound and soaks reaction 24 hours, obtains the described year super hydrophilic film of silver after taking out cleaning-drying; Wherein reducing agent consumption is 1.5 ~ 3 times of silver nitrate quality in silver ammino solution;
Described reducing agent is glucose, polyvinylpyrrolidone, sodium ascorbate, vitamin C, citric acid or natrium citricum.
Beneficial effect of the present invention is:
The present invention adopts blended and method that is inversion of phases film forming, and when utilizing inversion of phases between phase-separable material and material of main part, form the rough surface of micro/nano level, then membrane material is immersed in the solution containing DOPA compound and carries out surface modification, the oxidation of DOPA compound, autohemagglutination, feature effects on surface that is crosslinked, that adhere to is utilized to carry out the super hydrophilic film of modification preparation, the week reduction that further utilization gathers DOPA or poly-dopamine reduces to silver ion, is finally prepared the super hydrophilic membrane surfaces of load silver again by the reaction of DOPA compound.The ultra-hydrophilic surface of the ultra-hydrophilic surface utilizing the method to be formed and load silver thereof has lasting super hydrophilicity and antibiotic property.
Accompanying drawing explanation
Fig. 1 is the compound porous counterdie electron microscopic picture of Kynoar prepared by embodiment 1-3.
Fig. 2 is the super hydrophilic composite porous film electron microscopic picture of Kynoar prepared by embodiment 1-3.
Detailed description of the invention
Be further analyzed the present invention below in conjunction with specific embodiment, concrete steps are as follows:
(1) be the Kynoar of 5% ~ 20% by mass percent, mass percent is the phase-splitting polymer of 2% ~ 8%, mass percent be 1% ~ 5% aperture adjustment agent and mass percent be 67% ~ 92% solvent carry out dissolving and mix, obtain preparation liquid after vacuum defoamation; Enter coagulating bath after preparation liquid is become liquid film by scraper or extrusion die, 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) is immersed in the aqueous solution of DOPA compound soaks reaction 24 hours, obtain the super hydrophilic composite porous film of described Kynoar after taking out cleaning-drying, wherein in DOPA compound water solution, the mass percentage concentration of DOPA compound is 0.05 ~ 0.3 ﹪.
(3) super for the Kynoar obtained in step (2) hydrophilic composite porous film is immersed in silver ammino solution to react after 0.5 ~ 6 hour and adds reducing agent, continue reaction again 4 ~ 12 hours, the Kynoar composite porous film that silver is carried on surface is obtained after taking out cleaning, Kynoar composite porous film surface being carried silver is again immersed in the aqueous solution of DOPA compound and soaks reaction 24 hours, the described year super hydrophilic film of silver is obtained after taking out cleaning-drying, wherein, reducing agent consumption is 1.5 ~ 3 times of silver nitrate quality.
Described phase-splitting polymer is polyvinyl chloride, chliorinated polyvinyl chloride, polyvinyl chloride/-vinyl acetate co-polymer, polystyrene, polystyrene/copolymer-maleic anhydride, polysulfones, polyether sulfone, one or more mixing in polyacrylonitrile.Described solvent is one in DMF, DMA, trimethyl phosphate, triethyl phosphate, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE or mixed liquor arbitrarily.Described aperture adjustment agent is one or more in polyvinylpyrrolidone, polyethylene glycol, glycerine, diethylene glycol (DEG).Described DOPA compound is 3,4 dihydroxy benzenes alanines (DOPA), 4-(2-ethylamino-) benzene-1,2-glycol (dopamine).Described reducing agent is glucose, polyvinylpyrrolidone, sodium ascorbate, vitamin C, citric acid, natrium citricum.
According to above-mentioned a kind of compound aromatic micro-capsule and the preparation method carrying silver-colored aromatic micro-capsule thereof, describe the present invention in detail with specific embodiment below.The implementation step of all embodiments is identical with abovementioned steps.It should be noted that described embodiment is not construed as limiting the invention, all distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
First prepare compound aromatic micro-capsule, see specific embodiment:
Embodiment 1-1.
(1) quality is respectively the Kynoar of 5g, the phase-splitting polymer poly vinyl chloride of 2g, the aperture adjustment agent polyethylene glycol of 1g and the solvent DMF of 92g carry out dissolving and mix, and obtain preparation liquid after vacuum defoamation; Enter coagulating bath after preparation liquid is become liquid film by scraper, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar.
(2) the compound porous counterdie of Kynoar prepared in step (1) being immersed in mass percentage concentration is soak reaction 24 hours in 0.3 ﹪ DOPA compound water solution, obtains the super hydrophilic composite porous film of described Kynoar after taking out cleaning-drying.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-1 are less than 10 °, complete wetting in 1s.
Embodiment 1-2.
(1) quality is respectively the Kynoar of 20g, the phase-splitting polyether sulfone of 1g, phase-splitting polymers polystyrene/the copolymer-maleic anhydride of 3g, the aperture adjustment agent diethylene glycol (DEG) of 5g and the solvent N of 71g, N-dimethylacetylamide carries out dissolving and mixes, and obtains preparation liquid after vacuum defoamation; Enter coagulating bath after preparation liquid is become liquid film by extrusion die, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar.
(2) the compound porous counterdie of Kynoar prepared in step (1) being immersed in mass percentage concentration is soak reaction 24 hours in 0.2 ﹪ dopamine compound water solution, obtains the super hydrophilic composite porous film of described Kynoar after taking out cleaning-drying.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-2 are less than 10 °, complete wetting in 1s.
Embodiment 1-3.
(1) quality is respectively the Kynoar of 10g, the phase-splitting polymer polysulfones of 2g, the phase-splitting polymers polystyrene of 6g, the aperture adjustment agent polyvinylpyrrolidone of 1g, the aperture adjustment agent polyethylene glycol of 3g and the solvent N of 50g, N-dimethylacetylamide, the solvent triethyl phosphate of 28g carries out dissolving and mixes, and obtains preparation liquid after vacuum defoamation; Enter coagulating bath after preparation liquid is become liquid film by scraper, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar.
(2) the compound porous counterdie of Kynoar prepared in step (1) being immersed in mass percentage concentration is soak reaction 24 hours in 0.15 ﹪ dopamine compound water solution, obtains the super hydrophilic composite porous film of described Kynoar after taking out cleaning-drying.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-3 are less than 10 °, complete wetting in 1s.Obviously can see the phase-splitting microballoon that the compound porous counterdie surface of Kynoar exists the formation of phase-splitting polymer as shown in Figure 1, porous counterdie is through poly-dopamine modified microsphere surface generation significant change as shown in Figure 2.
Embodiment 1-4.
(1) quality is respectively the Kynoar of 15g, the phase-splitting polymer chliorinated polyvinyl chloride of 1g, the phase-splitting polymer poly vinyl chloride/-vinyl acetate co-polymer of 5g, the aperture adjustment agent glycerine of 1g, the aperture adjustment agent polyethylene glycol of 2g and the solvent N of 50g, dinethylformamide, the solvent trimethyl phosphate of 26g carries out dissolving and mixes, and obtains preparation liquid after vacuum defoamation; Enter coagulating bath after preparation liquid is become liquid film by extrusion die, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar.
(2) the compound porous counterdie of Kynoar prepared in step (1) being immersed in mass percentage concentration is soak reaction 24 hours in 0.05 ﹪ DOPA compound water solution, obtains the super hydrophilic composite porous film of described Kynoar after taking out cleaning-drying.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-4 are less than 10 °, complete wetting in 1s.
Embodiment 1-5.
(1) quality is respectively the Kynoar of 8g, the phase-splitting polymer poly acrylonitrile of 1g, phase-splitting polymers polystyrene/the copolymer-maleic anhydride of 2g, the aperture adjustment agent polyethylene glycol of 2g and the solvent N of 60g, N-dimethylacetylamide, the solvent dimethyl sulfoxide (DMSO) of 27g carries out dissolving and mixes, and obtains preparation liquid after vacuum defoamation; Enter coagulating bath after preparation liquid is become liquid film by scraper, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar.
(2) the compound porous counterdie of Kynoar prepared in step (1) being immersed in mass percentage concentration is soak reaction 24 hours in 0.25 ﹪ DOPA compound water solution, obtains the super hydrophilic composite porous film of described Kynoar after taking out cleaning-drying.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-5 are less than 10 °, complete wetting in 1s.
Embodiment 1-6.
(1) quality is respectively the Kynoar of 13g, the phase-splitting polyether sulfone of 2g, the phase-splitting polymer poly vinyl chloride/-vinyl acetate co-polymer of 3g, the aperture adjustment agent diethylene glycol (DEG) of 3g, 1g aperture adjustment agent polyethylene glycol, the solvent DMA of 70g, the solvent N-methyl pyrilidone of 8g carries out dissolving and mixes, and obtains preparation liquid after vacuum defoamation; Enter coagulating bath after preparation liquid is become liquid film by extrusion die, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar.
(2) the compound porous counterdie of Kynoar prepared in step (1) being immersed in mass percentage concentration is soak reaction 24 hours in 0.1 ﹪ dopamine compound water solution, obtains the super hydrophilic composite porous film of described Kynoar after taking out cleaning-drying.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-6 are less than 10 °, complete wetting in 1s.
Embodiment 1-7
(1) quality is respectively the Kynoar of 20g, the phase-splitting polymer chliorinated polyvinyl chloride of 8g, the aperture adjustment agent polyvinylpyrrolidone of 5g and the solvent DMF of 67g carry out dissolving and mix, and obtain preparation liquid after vacuum defoamation; Enter coagulating bath after preparation liquid is become liquid film by scraper, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar.
(2) the compound porous counterdie of Kynoar prepared in step (1) being immersed in mass percentage concentration is soak reaction 24 hours in 0.1 ﹪ DOPA compound water solution, obtains the super hydrophilic composite porous film of described Kynoar after taking out cleaning-drying.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-7 are less than 10 °, complete wetting in 1s.
Embodiment 1-8
Embodiment 1-7 experiment condition phase-splitting polymer chliorinated polyvinyl chloride is replaced with polyvinyl chloride/-vinyl acetate co-polymer, solvent N, dinethylformamide replaces with triethyl phosphate, aperture adjustment agent polyvinylpyrrolidone replaces with glycerine, other experiment conditions are constant, finally prepare the super hydrophilic composite porous film of Kynoar.The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-8 are less than 10 °, complete wetting in 1s.
Embodiment 1-9
Embodiment 1-7 experiment condition phase-splitting polymer chliorinated polyvinyl chloride is replaced with polystyrene, solvent N, dinethylformamide replaces with dimethyl sulfoxide (DMSO), aperture adjustment agent polyvinylpyrrolidone replaces with diethylene glycol (DEG), other experiment conditions are constant, finally prepare the super hydrophilic composite porous film of Kynoar.The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-9 are less than 10 °, complete wetting in 1s.
Embodiment 1-10
Embodiment 1-7 experiment condition phase-splitting polymer chliorinated polyvinyl chloride is replaced with polystyrene/copolymer-maleic anhydride, solvent N, dinethylformamide replaces with 1-METHYLPYRROLIDONE, and other experiment conditions are constant, finally prepares the super hydrophilic composite porous film of Kynoar.The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-10 are less than 10 °, complete wetting in 1s.
Embodiment 1-11
Embodiment 1-7 experiment condition phase-splitting polymer chliorinated polyvinyl chloride is replaced with polysulfones, and other experiment conditions are constant, finally prepare the super hydrophilic composite porous film of Kynoar.The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-11 are less than 10 °, complete wetting in 1s.
Embodiment 1-12
Embodiment 1-7 experiment condition phase-splitting polymer chliorinated polyvinyl chloride is replaced with polyether sulfone, and other experiment conditions are constant, finally prepare the super hydrophilic composite porous film of Kynoar.The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-12 are less than 10 °, complete wetting in 1s.
Embodiment 1-13
Embodiment 1-7 experiment condition phase-splitting polymer chliorinated polyvinyl chloride is replaced with polyacrylonitrile, and other experiment conditions are constant, finally prepare the super hydrophilic composite porous film of Kynoar.The 20 DEG C of water static contact angles in film surface prepared by embodiment 1-13 are less than 10 °, complete wetting in 1s.
Then utilize the super hydrophilic compound porous film preparation Kynoar of the Kynoar obtained in above-described embodiment to carry the super hydrophilic film of silver, see specific embodiment:
Embodiment 2-1.
Be immersed in after super for the Kynoar prepared to above-described embodiment 1-1 hydrophilic composite porous film is cut into 5cm × 5cm size in 100g silver ammino solution to react after 0.5 hour and add 3g reducing agent glucose, continue reaction again 4 hours, the Kynoar composite porous film that silver is carried on surface is obtained after taking out cleaning, Kynoar composite porous film surface being carried silver is again immersed in the aqueous solution of DOPA compound and soaks reaction 24 hours, the described year super hydrophilic film of silver is obtained after taking out cleaning-drying, wherein, in silver ammino solution, silver nitrate mass concentration is 2 ﹪, reducing agent consumption is 1.5 times of silver nitrate quality.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-1 are less than 10 °, complete wetting in 1s, are 99.9% to Escherichia coli sterilizing rate.
Embodiment 2-2.
Be immersed in after super for the Kynoar prepared to above-described embodiment 1-2 hydrophilic composite porous film is cut into 5cm × 5cm size in 100g silver ammino solution to react after 1 hour and add 6g reducing agent polyvinylpyrrolidone, continue reaction again 12 hours, the Kynoar composite porous film that silver is carried on surface is obtained after taking out cleaning, surface being carried the Kynoar composite porous film of silver, to be again immersed in mass percentage be soak reaction 24 hours in the aqueous solution of 0.2 ﹪ dopamine compound, the described year super hydrophilic film of silver is obtained after taking out cleaning-drying, wherein, in silver ammino solution, silver nitrate mass concentration is 2 ﹪, reducing agent consumption is 3 times of silver nitrate quality.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-2 are less than 10 °, complete wetting in 1s, are 99.8% to Escherichia coli sterilizing rate.
Embodiment 2-3.
Be immersed in after super for the Kynoar prepared to above-described embodiment 1-3 hydrophilic composite porous film is cut into 5cm × 5cm size in 100g silver ammino solution to react after 2 hours and add 4g reducing agent vitamin C, continue reaction again 6 hours, the Kynoar composite porous film that silver is carried on surface is obtained after taking out cleaning, surface being carried the Kynoar composite porous film of silver, to be again immersed in mass percentage be soak reaction 24 hours in the aqueous solution of 0.15 ﹪ dopamine compound, the described year super hydrophilic film of silver is obtained after taking out cleaning-drying, wherein, in silver ammino solution, silver nitrate mass concentration is 2 ﹪, reducing agent consumption is 2 times of silver nitrate quality.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-3 are less than 10 °, complete wetting in 1s, are 99.9% to Escherichia coli sterilizing rate.
Embodiment 2-4.
Be immersed in after super for the Kynoar prepared to above-described embodiment 1-4 hydrophilic composite porous film is cut into 5cm × 5cm size in 100g silver ammino solution to react after 5 hours and add 5g reducing agent sodium ascorbate, continue reaction again 8 hours, the Kynoar composite porous film that silver is carried on surface is obtained after taking out cleaning, surface being carried the Kynoar composite porous film of silver, to be again immersed in mass percentage be soak reaction 24 hours in the aqueous solution of 0.05 ﹪ DOPA compound, the described year super hydrophilic film of silver is obtained after taking out cleaning-drying, wherein, in silver ammino solution, silver nitrate mass concentration is 2 ﹪, reducing agent consumption is 2.5 times of silver nitrate quality.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-4 are less than 10 °, complete wetting in 1s, are 99.8% to Escherichia coli sterilizing rate.
Embodiment 2-5.
Be immersed in after super for the Kynoar prepared to above-described embodiment 1-5 hydrophilic composite porous film is cut into 5cm × 5cm size in 100g silver ammino solution to react after 3 hours and add 3g reducing agent citric acid, continue reaction again 10 hours, the Kynoar composite porous film that silver is carried on surface is obtained after taking out cleaning, surface being carried the Kynoar composite porous film of silver, to be again immersed in mass percentage be soak reaction 24 hours in the aqueous solution of 0.25 ﹪ DOPA compound, the described year super hydrophilic film of silver is obtained after taking out cleaning-drying, wherein, in silver ammino solution, silver nitrate mass concentration is 2 ﹪, reducing agent consumption is 1.5 times of silver nitrate quality.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-5 are less than 10 °, complete wetting in 1s, are 99.7% to Escherichia coli sterilizing rate.
Embodiment 2-6.
Be immersed in after super for the Kynoar prepared to above-described embodiment 1-6 hydrophilic composite porous film is cut into 5cm × 5cm size in 100g silver ammino solution to react after 2.5 hours and add 4g reducing agent natrium citricum, continue reaction again 10 hours, the Kynoar composite porous film that silver is carried on surface is obtained after taking out cleaning, surface being carried the Kynoar composite porous film of silver, to be again immersed in mass percentage be soak reaction 24 hours in the aqueous solution of 0.1 ﹪ dopamine compound, the described year super hydrophilic film of silver is obtained after taking out cleaning-drying, wherein, in silver ammino solution, silver nitrate mass concentration is 2 ﹪, reducing agent consumption is 2 times of silver nitrate quality.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-6 are less than 10 °, complete wetting in 1s, are 99.9% to Escherichia coli sterilizing rate.
Embodiment 2-7.
Be immersed in after super for the Kynoar prepared to above-described embodiment 1-7 hydrophilic composite porous film is cut into 5cm × 5cm size in 100g silver ammino solution to react after 6 hours and add 5g reducing agent polyvinylpyrrolidone, continue reaction again 12 hours, the Kynoar composite porous film that silver is carried on surface is obtained after taking out cleaning, surface being carried the Kynoar composite porous film of silver, to be again immersed in mass percentage be soak reaction 24 hours in the aqueous solution of 0.1 ﹪ DOPA compound, the described year super hydrophilic film of silver is obtained after taking out cleaning-drying, wherein, in silver ammino solution, silver nitrate mass concentration is 2 ﹪, reducing agent consumption is 2.5 times of silver nitrate quality.
The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-7 are less than 10 °, complete wetting in 1s, are 99.9% to Escherichia coli sterilizing rate.
Embodiment 2-8.
The super hydrophilic composite porous film of the Kynoar prepared by embodiment 1-7 in embodiment 2-7 replaces to the super hydrophilic composite porous film of Kynoar that embodiment 1-8 prepares, and other experiment conditions are constant, finally obtains carrying the super hydrophilic film of silver.The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-8 are less than 10 °, complete wetting in 1s, are 99.9% to Escherichia coli sterilizing rate.
Embodiment 2-9.
The super hydrophilic composite porous film of the Kynoar prepared by embodiment 1-7 in embodiment 2-7 replaces to the super hydrophilic composite porous film of Kynoar that embodiment 1-9 prepares, and other experiment conditions are constant, finally obtains carrying the super hydrophilic film of silver.The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-9 are less than 10 °, complete wetting in 1s, are 99.9% to Escherichia coli sterilizing rate.
Embodiment 2-10.
The super hydrophilic composite porous film of the Kynoar prepared by embodiment 1-7 in embodiment 2-7 replaces to the super hydrophilic composite porous film of Kynoar that embodiment 1-10 prepares, and other experiment conditions are constant, finally obtains carrying the super hydrophilic film of silver.The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-10 are less than 10 °, complete wetting in 1s, are 99.9% to Escherichia coli sterilizing rate.
Embodiment 2-11.
The super hydrophilic composite porous film of the Kynoar prepared by embodiment 1-7 in embodiment 2-7 replaces to the super hydrophilic composite porous film of Kynoar that embodiment 1-11 prepares, and other experiment conditions are constant, finally obtains carrying the super hydrophilic film of silver.The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-11 are less than 10 °, complete wetting in 1s, are 99.9% to Escherichia coli sterilizing rate.
Embodiment 2-12.
The super hydrophilic composite porous film of the Kynoar prepared by embodiment 1-7 in embodiment 2-7 replaces to the super hydrophilic composite porous film of Kynoar that embodiment 1-12 prepares, and other experiment conditions are constant, finally obtains carrying the super hydrophilic film of silver.The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-12 are less than 10 °, complete wetting in 1s, are 99.9% to Escherichia coli sterilizing rate.
Embodiment 2-13.
The super hydrophilic composite porous film of the Kynoar prepared by embodiment 1-7 in embodiment 2-7 replaces to the super hydrophilic composite porous film of Kynoar that embodiment 1-13 prepares, and other experiment conditions are constant, finally obtains carrying the super hydrophilic film of silver.The 20 DEG C of water static contact angles in film surface prepared by embodiment 2-13 are less than 10 °, complete wetting in 1s, are 99.9% to Escherichia coli sterilizing rate.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet application claims, all belongs to protection scope of the present invention.
Claims (9)
1. a preparation method for the super hydrophilic composite porous film of Kynoar, is characterized in that the method comprises the following steps:
Step (1), Kynoar, phase-splitting polymer, aperture adjustment agent, solvent are carried out dissolving and mix, after vacuum defoamation, obtain preparation liquid; Enter coagulating bath after preparation liquid is become liquid film by scraper or extrusion die, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar; Wherein the mass percentage of each raw material in preparation liquid is as follows: 5 ~ 20 ﹪ Kynoar, 2 ~ 8 ﹪ phase-splitting polymer, 1 ~ 5 ﹪ aperture adjustment agent, 67 ~ 92 ﹪ solvents;
Step (2), the compound porous counterdie of Kynoar of preparation in step (1) is immersed in the aqueous solution of DOPA compound and soaks reaction 24 hours, after taking out cleaning-drying, obtain the super hydrophilic composite porous film of described Kynoar.
2. Kynoar carries a preparation method for the super hydrophilic film of silver, it is characterized in that the method comprises the following steps:
Step (1), Kynoar, phase-splitting polymer, aperture adjustment agent, solvent are carried out dissolving and mix, after vacuum defoamation, obtain preparation liquid; Enter coagulating bath after preparation liquid is become liquid film by scraper or extrusion die, after solution inversion of phases and cleaning, obtain the compound porous counterdie of Kynoar; Wherein the mass percentage of each raw material in preparation liquid is as follows: 5 ~ 20 ﹪ Kynoar, 2 ~ 8 ﹪ phase-splitting polymer, 1 ~ 5 ﹪ aperture adjustment agent, 67 ~ 92 ﹪ solvents;
Step (2), the compound porous counterdie of Kynoar of preparation in step (1) is immersed in the aqueous solution of DOPA compound and soaks reaction 24 hours, after taking out cleaning-drying, obtain the super hydrophilic composite porous film of described Kynoar;
Step (3), super for the Kynoar obtained hydrophilic composite porous film is immersed in silver ammino solution to react after 0.5 ~ 6 hour adds reducing agent in step (2), continue reaction again 4 ~ 12 hours, the Kynoar composite porous film that silver is carried on surface is obtained after taking out cleaning, Kynoar composite porous film surface being carried silver is again immersed in the aqueous solution of DOPA compound and soaks reaction 24 hours, obtains the described year super hydrophilic film of silver after taking out cleaning-drying.
3. the preparation method of the super hydrophilic composite porous film of a kind of Kynoar as claimed in claim 1 or a kind of Kynoar according to claim 2 carry the preparation method of the super hydrophilic film of silver, and the phase-splitting polymer that it is characterized in that described in step (1) is one or more in polyvinyl chloride, chliorinated polyvinyl chloride, polyvinyl chloride/-vinyl acetate co-polymer, polystyrene, polystyrene/copolymer-maleic anhydride, polysulfones, polyether sulfone, polyacrylonitrile.
4. the preparation method of the super hydrophilic composite porous film of a kind of Kynoar as claimed in claim 1 or a kind of Kynoar according to claim 2 carry the preparation method of the super hydrophilic film of silver, it is characterized in that the solvent described in step (1) is N, one or more mixed liquors in dinethylformamide, DMA, trimethyl phosphate, triethyl phosphate, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE.
5. the preparation method of the super hydrophilic composite porous film of a kind of Kynoar as claimed in claim 1 or a kind of Kynoar according to claim 2 carry the preparation method of the super hydrophilic film of silver, and the aperture adjustment agent that it is characterized in that described in step (1) is one or more in polyvinylpyrrolidone, polyethylene glycol, glycerine, diethylene glycol (DEG).
6. the preparation method of the super hydrophilic composite porous film of a kind of Kynoar as claimed in claim 1 or a kind of Kynoar according to claim 2 carry the preparation method of the super hydrophilic film of silver, it is characterized in that the DOPA compound described in step (2) is 3,4 dihydroxy benzenes alanines (DOPA) or 4-(2-ethylamino-) benzene-1,2-glycol (dopamine).
7. the preparation method of the super hydrophilic composite porous film of a kind of Kynoar as claimed in claim 1 or a kind of Kynoar according to claim 2 carry the preparation method of the super hydrophilic film of silver, it is characterized in that the mass percentage concentration of DOPA compound in step (2) DOPA compound water solution is 0.05 ~ 0.3 ﹪.
8. a kind of Kynoar as claimed in claim 2 carries the preparation method of the super hydrophilic film of silver, it is characterized in that the reducing agent described in step (3) is glucose, polyvinylpyrrolidone, sodium ascorbate, vitamin C, citric acid or natrium citricum.
9. a kind of Kynoar as claimed in claim 2 carries the preparation method of the super hydrophilic film of silver, it is characterized in that step (3) reducing agent consumption is 1.5 ~ 3 times of silver nitrate quality in silver ammino solution.
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