CN105597578A - Antibacterial separating membrane with directionally induced and loaded nano-silver and preparation method of antibacterial separating membrane - Google Patents
Antibacterial separating membrane with directionally induced and loaded nano-silver and preparation method of antibacterial separating membrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/28—Polymers of vinyl aromatic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Abstract
The invention belongs to the technical field of preparation of membrane materials and discloses an antibacterial separating membrane with directionally induced and loaded nano-silver and a preparation method of the antibacterial separating membrane. The preparation method comprises steps as follows: a macromolecule membrane forming material, an amphiphilic block polymer and a pore forming agent are dissolved in a solvent, a membrane casting solution is prepared, subjected to knifing or spinning membrane forming and then immersed in distilled water to be solidified, an ultrafiltration membrane is obtained, then soaked in a Ag[(NH3)2]<+> solution, taken out and air-dried after reacting and then added to a polyvinylpyrrolidone aqueous solution, a reducing agent solution is dropwise added for a reaction, and the antibacterial separating membrane is obtained through washing and drying finally. According to the membrane, polycarboxylic acid, sulfonic acid and the like are used as seeds, nano-silver is induced and loaded directionally on the surface of the membrane under electrostatic and chelating actions, the bonding strength of the nano-silver and the separating membrane is enhanced, agglomeration of the nano-silver is reduced, and the prepared separating membrane has the excellent antibacterial property and has the antibacterial property higher than 99.99% for Escherichia coli and Staphylococcus aureus.
Description
Technical field
The invention belongs to membrane material preparing technical field, be specifically related to a kind of directional induction loading nano silvery antibacterialDiffusion barrier and preparation method thereof.
Background technology
Membrane separation technique has obtained very large development in the application of water treatment, and wherein hyperfiltration technique is because of its energy consumptionRelatively low, environmental protection has a wide range of applications in separation is concentrated. In at present conventional membrane material,The macromolecular materials such as polysulfones, polyether sulfone, polyvinyl chloride, Kynoar have good mechanical performance, heatStability, resistance to acids and bases, good film forming characteristics, low price, is conventional film forming in membrane material preparationMaterial.
Bacterium and microorganism are the one of the main reasons that causes film to pollute to the pollution of film, have and pollute front difficulty in advanceThe rear difficult feature of cleaning of anti-, pollution. Even most of microorganism is killed in pretreatment, remaining work micro-Biology can be rapidly forms biomembrane on film surface, and biomembranous feature is that adhesion is strong, is not easy by clearlyRemove, in the time that membrane biological pollution acquires a certain degree, film will be difficult to continue operation, must clean just filmCan make the strainability of film be restored. Membrane biological pollution not only causes reduction, the effluent quality of effluent fluxThe increase of deteriorated, energy consumption, also shortened the service life of film, so prevent that bacterium and microorganism are to filmPollution and damage are still one and are difficult to solve vital problem.
At present, the research of antibacterial ultrafiltration membrane obtains certain progress. A lot of researchers are by membrane surface modification and commonMixed modification, prepares the antibacterial ultrafiltration membrane of different performance. Basri etc. pass through AgNO3, polyvinylpyrrolidone
(PVP), polyether sulfone (PES) blend is by AgNO3Load on milipore filter, by the antibacterial ability of AgMake film possess very strong antibiotic property. Yao etc. utilize the initiation of ultraviolet light at the pretreated film table of plasmaFace graft copolymerized 4-vinyl pyridine, and to the pyridine groups of grafting carry out quaternized and obtain antibacterial ultrafiltration membrane. HighScientific principle wait by ultra-violet radiation by Capsaicin derivatives graft on PES milipore filter film surface, studies have shown that milipore filterPossess good biocidal property, organic matter sterilization instant effect, sterilizing rate are high, and are not easy to lose.
China also obtains greater advance in the research of antibacterial ultrafiltration membrane, mainly studies surface of concentration grafting and blend and changesThe aspects such as property. However, to the research of antibacterial PES milipore filter still in the starting stage, by plasma,The methods such as uv photo initiated grafting are processed film surface, and former film is caused to destruction to a certain degree, and active group existsFilm surface distributed is inhomogeneous, and easily comes off. And the blending and modifying of membrane material, blending antibacterial agent in film,Can affect hydrophily, mechanical strength and the heat endurance of film. Therefore, how by the advantage of membrane material and antibacterialThe strong bonded of agent is got up, when reducing film pollution by interpolation antiseptic modified high-molecular membrane material,Make film there is good resistance leachability and resistance tocrocking is the emphasis of studying from now on.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the present invention is to provide onePlant the preparation method of the antibacterial diffusion barrier of directional induction loading nano silvery. The method is with Amphipathilic block polymerBe seed containing polycarboxylic acids, sulfonic acid group etc., induction generates the suspended nano silver of strong bonded at film near surface.
Another object of the present invention is again in providing a kind of directional induction load preparing by following method to receiveThe silver-colored antibacterial diffusion barrier of rice.
The present invention is achieved through the following technical solutions:
A preparation method for the antibacterial diffusion barrier of directional induction loading nano silvery, comprises following preparation process:
(1) macromolecule filming material, Amphipathilic block polymer and pore former are dissolved in solvent,At 50～80 DEG C, be uniformly mixed and deaeration, be made into casting solution;
(2), by step (1) gained casting solution knifing or carry out spinning film forming, be immersed into subsequently in distilled waterSolidify, after drying, obtain milipore filter;
(3) fixed point is induced in conjunction with silver ion: step (2) gained milipore filter is immersed in to Ag[(NH3)2]+MoltenIn liquid, after reaction 0.5～1h, take out and dry;
(4) under room temperature, step (3) gained milipore filter is joined to polyethylene of dispersing agent pyrrolidones (PVP)In the aqueous solution, then drip reductant solution stirring reaction;
(5) preparation of Nano Silver diffusion barrier: by dry through washing step (4) gained milipore filter, get final productTo the antibacterial diffusion barrier of directional induction loading nano silvery.
Preferably, described macromolecule filming material is polysulfones, polyether sulfone, polyvinyl chloride, KynoarDeng macromolecular material.
Described Amphipathilic block polymer be preferably poly acrylic acid-poly styrene (PAA-b-PS) block copolymer,Polymethyl methacrylate-polyacrylic acid (PMMA-b-PAA) block copolymer, sulfonic benzo ethene-diethylAlkenyl benzene polymer; Hydrophilic radical in described Amphipathilic block polymer (polyacrylic acid or sulfonic group) rubsYou are no less than 50% by content.
Described pore former is preferably polyvinyl alcohol or polypyrrole alkane ketone; Described solvent is preferably N-crassitudeKetone (NMP), DMF (DMF) or DMA (DMAC).
Preferably, described in step (1), in casting solution, each constituent mass percentage composition is: macromolecule filming materialMaterial 20%～25%, Amphipathilic block polymer 3%～5%, pore former 5%～10%, all the other are solvent.
Preferably, the Ag[(NH described in step (3)3)2]+The mass concentration of solution is 0.2%～0.8%; InstituteState milipore filter and Ag[(NH3)2]+The mass ratio of solution is 1:(3～8).
Preferably, the mass body volume concentrations of the polyvinylpyrrolidone aqueous solution described in step (4) is1%～5%; The mass ratio of described milipore filter and the polyvinylpyrrolidone aqueous solution is 1:(3～8).
Preferably, described in step (4), reducing agent is sodium borohydride or glucose, the concentration of reductant solutionBe 0.1～0.5mol/L.
Preferably, described in step (5), wash dry process as follows: use successively deionized water and anhydrous secondThe each washing of alcohol 2～3 times, until system pH is put into vacuum drying chamber after approaching neutrality, at 50～70 DEG CVacuum drying 1～3h.
The antibacterial diffusion barrier of a kind of directional induction loading nano silvery, prepares by above method.
Principle of the present invention is:
The diffusion barrier of being prepared film surface and had amphipathic Block copolymer by dry-wet method, makes amphipathic blockThe hydrophobic side of formula macromolecular compound is embedded in the hydrophobic material of film, and the parent of amphipathic Block copolymerWater base group (group such as polycarboxylic acids, sulfonic acid) is relatively evenly distributed on film surface; Poly-with amphipathic blocked againIn compound, polycarboxylic acids, sulfonic acid group etc. are seed, by the electronegative anionic group such as polycarboxylic acids, sulfonic acidSilver ion (Ag[(NH with positively charged3)2]+) static, chelation, in film surface orientation induction loadSilver ion; Finally, by tetrahydro boron sodium, glucose etc., silver ion reduction is become to Nano Silver, realize and separatingThe surface orientation loading nano silvery of membrane material, prepares that Nano Silver is evenly distributed and separates in conjunction with firmly carrying silverFilm, its preparation flow figure and directional induction loading nano silvery schematic diagram are respectively as depicted in figs. 1 and 2.
In dry-wet method film forming procedure, hydrophily base in hydrone and amphipathic Block copolymer in coagulating bathInteraction between group's groups such as () polycarboxylic acids, sulfonic acid, makes amphiphilic macromolecule have the coagulating bath of being dissolved inTendency, in wet method film forming procedure, the trend of oriented film external migration, along with casting solution is solid in coagulating bathChange, amphiphilic macromolecule is fixed on the surface of film, and hydrophobic one end is embedded in the hydrophobic material of film, hydrophilicOutwards stretch one end, be relatively evenly distributed on the surface of film, and the hydrophilic radicals such as polycarboxylic acids, sulfonic acid is outsideStretching, extension has improved the hydrophilicity of film. And the hydrophilic radicals such as polycarboxylic acids, sulfonic acid are elecrtonegativity, silver ion(Ag[(NH3)2]+) positively charged, static by electronegative sulfonic acid group etc. and electropositive silver ion,Chelation, taking the group such as polycarboxylic acids, sulfonic acid as seed, makes silver ion be evenly distributed on film surface. Connect, by reducing process, the Nano Silver that is simple substance by silver ion reduction, forms relatively steady on the surface of membrane materialFixed Nano Silver, realizes the preparation object of seed directional induction loading nano silvery diffusion barrier.
With respect to prior art, tool of the present invention has the following advantages and beneficial effect:
(1) the present invention adopts Seed inducement method at film surface orientation loading nano silvery, can control Nano Silver and existThe distribution on film surface;
(2) the present invention by the hydrophilic radical of amphipathic Block copolymer groups such as () polycarboxylic acids, sulfonic acid allThe even film surface that is distributed in, taking polycarboxylic acids, sulfonic acid etc. as seed, the Nano Silver that induction generates is in film surface distributedEvenly, prevent Nano Silver agglomeration;
(3) the present invention is by the silver ion of the electronegative anionic groups such as polycarboxylic acids, sulfonic acid and positively charged(Ag[(NH3)2]+) static, chelation, both are in conjunction with firmly, the Nano Silver of preparation is not easy to come off,Reduce the loss of Nano Silver;
(4) in the present invention, amphiphilic block polymer hydrophobic section embeds film inside, and its hydrophilic section can be toThe overhanging spread of film becomes hydrophily stretched wire, and fixed point combining nano silver, to the water flux of film with hold back properties influence ratioLess;
(5) the loading nano silvery diffusion barrier that prepared by the present invention, good anti-bacterial effect, for Escherichia coli and golden yellowLook staphylococcic antibiotic property > 99.99%;
(6) in the present invention, adopt Seed inducement oriented load Nano Silver, be combined firmly with film, and silverAddition is few, and cost is low, and the diffusion barrier making has good anti-microbial property, has effectively extended making of filmWith the life-span, simple for process, contamination resistance strengthens greatly.
Brief description of the drawings
Fig. 1 is the preparation flow figure of the antibacterial diffusion barrier of directional induction loading nano silvery of the present invention;
Fig. 2 is the schematic diagram of directional induction loading nano silvery of the present invention;
Fig. 3 is the XRD diffraction pattern of the embodiment of the present invention 1 gained nanometer silver antimicrobial diffusion barrier.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but enforcement side of the present inventionFormula is not limited to this.
Embodiment 1
(1) get 20g polysulfones and add in 72gDMF, stir 4h at 60 DEG C, until polysulfones dissolves completely,In solution, add 3gPAA-b-PS (Li Guanghua, Yang Pingping etc., amphipathic nature block polymer respectively againSynthetic and the micellar conformation of PAA-b-PS) block copolymer and 5g polyvinyl alcohol, at 60 DEG C, stir 24h,After vacuum defoamation, at 60 DEG C, leave standstill 24h, form casting solution;
(2) casting solution after deaeration is spread on glass plate to 30um thick film with scraper, in air, stopStay 10s, after be immersed into film-forming in distilled water, at room temperature dry, preparation has an amphipathic block polymerizationThe diffusion barrier of thing;
(3) get above flat sheet membrane 8g, the mass fraction that is immersed in 40g is 0.2% silver ion (Ag[(NH3)2]+)In solution, after reaction 1h, taking-up is dried;
(4), under room temperature, by the above diffusion barrier in conjunction with silver ion, being immersed in concentration is the poly-second of 5% (m/v)In alkene pyrrolidone (PVP) aqueous solution; Under magnetic agitation, then (concentration is 0.1 by 3ml sodium borohydrideMol/L) be added drop-wise in mixed solution with the speed of 30 per minute, drip rear continuation stirring until hydrogenDischarge completely;
(5) take out diffusion barrier, with deionized water washing 3 times, then with absolute ethyl alcohol washing 3 times, until bodyBe that pH value approaches neutrality; Then sample is put into vacuum drying chamber, temperature is slowly risen to 70 DEG C from 50 DEG C,Then vacuum drying 2h at 70 DEG C, can obtain the antibacterial diffusion barrier of directional induction loading nano silvery.
The XRD diffraction pattern of the present embodiment gained nanometer silver antimicrobial diffusion barrier as shown in Figure 3. As seen from Figure 3Significantly Ag characteristic peak.
Embodiment 2
(1) get 25g polysulfones and add in 60gDMF, stir 4h at 60 DEG C, until polysulfones dissolves completely,In solution, add 5gPAA-b-PS block copolymer and 10g polyvinyl alcohol respectively again, at 60 DEG C, stir24h leaves standstill 24h at 60 DEG C after vacuum defoamation, form casting solution;
Step (2)～(5) are with embodiment 1, obtain antibacterial point of the directional induction loading nano silvery of the present embodimentFrom film.
Embodiment 3
Step (1) is with embodiment 1
(2), by the casting solution after deaeration, at 60 DEG C, carry out dry-wet spinning by plug-in type spinneret.Core liquid is pure water, and spinneret is apart from the distance 20cm of solidification liquid, and solidification liquid is the mixed liquor of solvent and water(DMF: water=1:1, mass ratio), 120 ms/min of draw speeds. Obtain new life's by above do-wet methodHollow-fibre membrane, then clean except desolventizing through pure water, then, after ethanol cleans, dry at 80 DEG CDry one-tenth polyacrylonitrile doughnut, doughnut internal diameter 0.3～0.4mm, external diameter 0.5～0.6mm;
Step (3)～(5) are with embodiment 1, obtain antibacterial point of the directional induction loading nano silvery of the present embodimentFrom film.
Embodiment 4
Step (1)～(2) are with embodiment 1
(3) get above flat sheet membrane 8g, the mass fraction that is immersed in 40g is 0.8% silver ion (Ag[(NH3)2]+)In solution, after reaction 1h, taking-up is dried;
(4), under room temperature, by the above diffusion barrier in conjunction with silver ion, being immersed in concentration is the poly-second of 5% (m/v)In alkene pyrrolidone (PVP) aqueous solution; Under magnetic agitation, then (concentration is 0.5 by 2.4ml sodium borohydrideMol/L) be added drop-wise in mixed solution with the speed of 30 per minute, drip rear continuation stirring until hydrogenDischarge completely;
Step (5), with embodiment 1, obtains the antibacterial diffusion barrier of directional induction loading nano silvery of the present embodiment.
Embodiment 5
(1) get 20g polyether sulfone and add in 72gDMF, stir 4h at 60 DEG C, until polyether sulfone is completeDissolve, then to adding 3gPMMA-b-PAA in solution, (Li Aihua, Liu Jingquan etc. pass through RAFT respectivelyLegal system is for amphiphilic diblock copolymer and induction self assembly behavior) block copolymer and 5g polyvinyl alcohol,At 60 DEG C, stir 24h, after vacuum defoamation, at 60 DEG C, leave standstill 24h, form casting solution;
Step (2) is with embodiment 1;
(3) get above flat sheet membrane 8g, the mass fraction that is immersed in 40g is 0.8% silver ion (Ag[(NH3)2]+)In solution, after reaction 1h, taking-up is dried;
(4), under room temperature, by the above diffusion barrier in conjunction with silver ion, being immersed in concentration is the poly-second of 5% (m/v)In alkene pyrrolidone (PVP) aqueous solution; Under magnetic agitation, then (concentration is 0.5 by 2.4ml sodium borohydrideMol/L) be added drop-wise in mixed solution with the speed of 30 per minute, drip rear continuation stirring until hydrogenDischarge completely;
Step (5), with embodiment 1, obtains the antibacterial diffusion barrier of directional induction loading nano silvery of the present embodiment.
Embodiment 6
(1) get 23g Kynoar and add in 66gDMF, stir 4h at 60 DEG C, until PVDFDissolve completely, then in solution, add 4gPMMA-b-PAA block copolymer and 7g polyvinyl alcohol respectively,At 60 DEG C, stir 24h, after vacuum defoamation, at 60 DEG C, leave standstill 24h, form casting solution;
(2), by the casting solution after deaeration, at 60 DEG C, carry out dry-wet spinning by plug-in type spinneret.Core liquid is pure water, and spinneret is apart from the distance 20cm of solidification liquid, and solidification liquid is the mixed liquor of solvent and water(DMF: water=1:1, mass ratio), 120 ms/min of draw speeds. Obtain new life's by above do-wet methodHollow-fibre membrane, then clean except desolventizing through pure water, then, after ethanol cleans, dry at 80 DEG CDry one-tenth polyacrylonitrile doughnut, doughnut internal diameter 0.3～0.4mm, external diameter 0.5～0.6mm;
(3) get above flat sheet membrane 8g, the mass fraction that is immersed in 40g is 0.5% silver ion (Ag[(NH3)2]+)In solution, after reaction 1h, taking-up is dried;
(4), under room temperature, by the above diffusion barrier in conjunction with silver ion, being immersed in concentration is the poly-second of 5% (m/v)In alkene pyrrolidone (PVP) aqueous solution; Under magnetic agitation, then (concentration is 0.25 by 3ml sodium borohydrideMol/L) be added drop-wise in mixed solution with the speed of 30 per minute, drip rear continuation stirring until hydrogenDischarge completely;
Step (5), with embodiment 1, obtains the antibacterial diffusion barrier of directional induction loading nano silvery of the present embodiment.
Implementation result
Taking polysulphone super-filter membrane as blank, by the embodiment of the present invention 1～6 gained nanometer silver antimicrobial diffusion barrier andBlank film is put into respectively without cingula plug wide-mouth bottle, drips seed liquor, in adding after 1h at membrane surfaceAcid phosphate buffer solution washs vibration, gets eluent and does gradient dilution, gets 0.1mL spread plate, 37 DEG CLower cultivation 48h, counts the clump count in culture dish, calculates antibiotic rate, and test bacterial classification is large intestine barBacterium ATCC25922, staphylococcus aureus ATCC6538. Result is as shown in table 1.
Table 1 antibacterial experiment testing result
As can be seen from Table 1, within very short action time, the antibacterial separation of gained loading nano silvery of the present inventionFilm has splendid inhibition to Escherichia coli and staphylococcus aureus, antibiotic rate all 99.99% withUpper, this loading nano silvery diffusion barrier, can be for common in environment within the scope of certain microorganism concnMicroorganism accomplish to suppress completely.
Above-described embodiment is preferably embodiment of the present invention, but embodiments of the present invention are not subject to above-mentioned realityExecute routine restriction, other any do not deviate from the change done under Spirit Essence of the present invention and principle, modification,Substitute, combine, simplify, all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a preparation method for the antibacterial diffusion barrier of directional induction loading nano silvery, is characterized in that comprising followingPreparation process:
(1) macromolecule filming material, Amphipathilic block polymer and pore former are dissolved in solvent,At 50～80 DEG C, be uniformly mixed and deaeration, be made into casting solution;
(2), by step (1) gained casting solution knifing or carry out spinning film forming, be immersed into subsequently in distilled waterSolidify, after drying, obtain milipore filter;
(3) fixed point is induced in conjunction with silver ion: step (2) gained milipore filter is immersed in to Ag[(NH3)2]+MoltenIn liquid, after reaction 0.5～1h, take out and dry;
(4) under room temperature, step (3) gained milipore filter is joined to the polyethylene of dispersing agent pyrrolidones aqueous solutionIn, then drip reductant solution stirring reaction;
(5) preparation of Nano Silver diffusion barrier: by dry through washing step (4) gained milipore filter, get final productTo the antibacterial diffusion barrier of directional induction loading nano silvery.
2. the preparation method of the antibacterial diffusion barrier of a kind of directional induction loading nano silvery according to claim 1,It is characterized in that: described macromolecule filming material is polysulfones, polyether sulfone, polyvinyl chloride or Kynoar.
3. the preparation method of the antibacterial diffusion barrier of a kind of directional induction loading nano silvery according to claim 1,It is characterized in that: described Amphipathilic block polymer is poly acrylic acid-poly styrene block copolymer, poly-methylMethyl acrylate-polyacrylic acid block copolymer or sulfonic benzo ethene-divinyl benzene polymers; Described amphiphilicIn property block polymer, hydrophilic radical molar content is no less than 50%.
4. the preparation method of the antibacterial diffusion barrier of a kind of directional induction loading nano silvery according to claim 1,It is characterized in that: described pore former is polyvinyl alcohol or polypyrrole alkane ketone; Described solvent is N-crassitudeKetone, DMF or DMA.
5. the preparation method of the antibacterial diffusion barrier of a kind of directional induction loading nano silvery according to claim 1,It is characterized in that: in described casting solution, each constituent mass percentage composition is: macromolecule filming material 20%～25%,Amphipathilic block polymer 3%～5%, pore former 5%～10%, all the other are solvent.
6. the preparation method of the antibacterial diffusion barrier of a kind of directional induction loading nano silvery according to claim 1,It is characterized in that: the Ag[(NH described in step (3)3)2]+The mass concentration of solution is 0.2%～0.8%; InstituteState milipore filter and Ag[(NH3)2]+The mass ratio of solution is 1:(3～8).
7. the preparation method of the antibacterial diffusion barrier of a kind of directional induction loading nano silvery according to claim 1,It is characterized in that: the mass body volume concentrations of the polyvinylpyrrolidone aqueous solution described in step (4) is1%～5%; The mass ratio of described milipore filter and the polyvinylpyrrolidone aqueous solution is 1:(3～8).
8. the preparation method of the antibacterial diffusion barrier of a kind of directional induction loading nano silvery according to claim 1,It is characterized in that: described in step (4), reducing agent is sodium borohydride or glucose, the concentration of reductant solutionBe 0.1～0.5mol/L.
9. the preparation method of the antibacterial diffusion barrier of a kind of directional induction loading nano silvery according to claim 1,It is characterized in that washing described in step (5) dry process as follows: use successively deionized water and absolute ethyl alcoholEach washing 2～3 times, until system pH is put into vacuum drying chamber after approaching neutrality, true at 50～70 DEG CEmpty dry 1～3h.
10. the antibacterial diffusion barrier of directional induction loading nano silvery, is characterized in that: by claim 1～9Method described in any one prepares.
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Cited By (4)
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| CN106215724A (en) * | 2016-07-28 | 2016-12-14 | 华南理工大学 | A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof |
| CN108325398A (en) * | 2018-02-07 | 2018-07-27 | 江苏理工学院 | A kind of preparation method of pollution-resistant membrane material |
| CN110841492A (en) * | 2019-09-25 | 2020-02-28 | 长春工业大学 | Preparation method of nano-silver modified polytetrafluoroethylene microporous membrane for membrane distillation |
| CN115155336A (en) * | 2022-07-15 | 2022-10-11 | 南昌航空大学 | Photoreduction deposition nano-silver antibacterial polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
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| CN104028123A (en) * | 2014-05-14 | 2014-09-10 | 浙江大学 | Preparation method for polymer nanofiber separation membrane |
| CN104190274A (en) * | 2014-09-19 | 2014-12-10 | 福州大学 | Antibacterial polyvinylidene fluoride membrane and preparation method thereof |
| CN104226124A (en) * | 2014-08-12 | 2014-12-24 | 江苏鸿典投资股份有限公司 | Polyvinylidene fluoride membrane and preparation method thereof |
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| CN104028123A (en) * | 2014-05-14 | 2014-09-10 | 浙江大学 | Preparation method for polymer nanofiber separation membrane |
| CN104226124A (en) * | 2014-08-12 | 2014-12-24 | 江苏鸿典投资股份有限公司 | Polyvinylidene fluoride membrane and preparation method thereof |
| CN104190274A (en) * | 2014-09-19 | 2014-12-10 | 福州大学 | Antibacterial polyvinylidene fluoride membrane and preparation method thereof |
| CN104888623A (en) * | 2015-06-04 | 2015-09-09 | 浙江纺织服装职业技术学院 | Polyvinylidene fluoride super-hydrophilic composite porous membrane and preparation method of silver-loaded super-hydrophilic membrane thereof |
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| CN106215724A (en) * | 2016-07-28 | 2016-12-14 | 华南理工大学 | A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof |
| CN108325398A (en) * | 2018-02-07 | 2018-07-27 | 江苏理工学院 | A kind of preparation method of pollution-resistant membrane material |
| CN110841492A (en) * | 2019-09-25 | 2020-02-28 | 长春工业大学 | Preparation method of nano-silver modified polytetrafluoroethylene microporous membrane for membrane distillation |
| CN115155336A (en) * | 2022-07-15 | 2022-10-11 | 南昌航空大学 | Photoreduction deposition nano-silver antibacterial polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
| CN115155336B (en) * | 2022-07-15 | 2023-06-23 | 南昌航空大学 | Photo-reduction deposited nano-silver antibacterial polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
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