CN106215724A - A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof - Google Patents

A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof Download PDF

Info

Publication number
CN106215724A
CN106215724A CN201610609458.6A CN201610609458A CN106215724A CN 106215724 A CN106215724 A CN 106215724A CN 201610609458 A CN201610609458 A CN 201610609458A CN 106215724 A CN106215724 A CN 106215724A
Authority
CN
China
Prior art keywords
filtering film
loading nano
nano silvery
composite nanometer
nanometer filtering
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610609458.6A
Other languages
Chinese (zh)
Inventor
肖凯军
朱子沛
易立中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GUANGZHOU JASON MEMBRANE TECHNOLOGY Co Ltd
South China University of Technology SCUT
Original Assignee
GUANGZHOU JASON MEMBRANE TECHNOLOGY Co Ltd
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GUANGZHOU JASON MEMBRANE TECHNOLOGY Co Ltd, South China University of Technology SCUT filed Critical GUANGZHOU JASON MEMBRANE TECHNOLOGY Co Ltd
Priority to CN201610609458.6A priority Critical patent/CN106215724A/en
Publication of CN106215724A publication Critical patent/CN106215724A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention belongs to technology field of membrane materials, disclose a kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof.Described preparation method is: with concentrated sulphuric acid, PES sulfonation is obtained SPES, SPES and pore former is dissolved in a solvent, is made into knifing after casting solution, obtains ultrafilter membrane after solidification；Then gained ultrafilter membrane is immersed in Ag [(NH3)2]+In solution, load combines silver ion, generates nanometer silver by reducing agent reduction；Gained ultrafilter membrane is immersed into successively in the hexane solution of m-diaminobenzene. aqueous solution and pyromellitic trimethylsilyl chloride reaction again, takes out and dry after-baking, obtain the antibacterial composite nanometer filtering film of described loading nano silvery.The present invention generates complex functional layer by oriented load nanometer silver and by interfacial polymerization, and gained composite nanometer filtering film anti-microbial property is good and anti-microbial property is lasting.

Description

A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof
Technical field
The invention belongs to technology field of membrane materials, be specifically related to a kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation thereof Method.
Background technology
Polyether sulfone (PES) has good acid and alkali-resistance, compression resistance ability, and mechanical and thermal properties is stable, good film-forming property, Being a kind of good material of preparing, the fields such as the filter membrane with PES as raw material processes at water, food processing, biological medicine have extensively General application.But PES hydrophilic is poor, easily produces fouling membrane during use, cause film properties to decline, affect the use of film Life-span.
But during the use of filter membrane, meeting is by microorganism adsorption, and then growth and breeding forms biosphere, blocks film Hole, makes the cutoff performance of film reduce, and has a strong impact on the service life of film.Therefore introduce the most antibacterial on membrane material Agent, kills the absorption microorganism on film surface in time, is a kind of effective way improving film contamination resistance.Conventional antibacterial In agent, nanometer silver is one of study hotspot.Nanometer silver is a kind of broad spectrum antimicrobicide, and the microorganism in environment can be produced by extremely low concentration Raw good inhibition, is a kind of efficient anti-biotic material.
The at present preparation method of the membrane material of loading nano silvery, mainly by nanometer silver is blended with filmogen or Prepared by surface adsorption silver ion.Although it is simple that technique is directly blended, it is easy to operation, but owing to inorganic nanometer silver is having , easily there is the phenomenon that nanometer silver is reunited, and is blended very difficult that nanometer silver is rich in poor compatibility in the macromolecule filming material of machine Collection is on the surface of film so that antibacterial effect is undesirable；And by surface adsorption by nano-silver loaded on film surface, table can be made in Face is enriched with, and Load Balanced, but nanometer silver is weak with the active force of film, in use runs off too fast so that antibacterial effect The most lasting.
Summary of the invention
In place of solving the shortcoming and defect of above prior art, the primary and foremost purpose of the present invention is to provide a kind of load The preparation method of nanometer silver antimicrobial composite nanometer filtering film.The method is intended to the surface modification to filter membrane, by the effect of chemical bond, and will Nanometer silver is combined in the surface of film, then by interfacial polymerization, in one layer of fine and close functional layer of surface aggregate of ultrafilter membrane, makes film There is the performance of nanofiltration, the nanometer silver of load is effectively embedded simultaneously, prevent nanometer silver to run off.
Another object of the present invention is to provide a kind of loading nano silvery prepared by said method antibacterial compound NF membrane.Gained loading nano silvery antibacterial composite nanometer filtering film antibiotic property is lasting, and antifouling property and service life are improved.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of the antibacterial composite nanometer filtering film of loading nano silvery, including following preparation process:
(1) with concentrated sulphuric acid by PES sulfonation, sulfonated polyether sulfone (SPES) is obtained；SPES and pore former are dissolved in a solvent, It is uniformly mixed at 50～80 DEG C and deaeration, is made into casting solution；
(2) by step (1) gained casting solution knifing, then it is immersed in distilled water solidification, after drying, obtains ultrafilter membrane；
(3) load combines silver ion: step (2) gained ultrafilter membrane is immersed in Ag [(NH3)2]+In solution, react 1～2h Rear taking-up is dried；
(4) being immersed in deionized water by step (3) gained ultrafilter membrane under room temperature, then dropping reductant solution generates and receives Meter Yin；
(5) washing of step (4) gained ultrafilter membrane being dried, be then immersed in m-diaminobenzene. aqueous solution reaction, taking-up is dried in the air Dry, then be immersed in the hexane solution of pyromellitic trimethylsilyl chloride reaction, taking-up dry after at 50～80 DEG C heat treatment 10～ 15min, obtains the antibacterial composite nanometer filtering film of described loading nano silvery.
Described in step (1), pore former is preferably polyvinyl alcohol or polyvinylpyrrolidone；Described solvent is preferably N-first Base ketopyrrolidine (NMP), N,N-dimethylformamide (DMF) or DMAC N,N' dimethyl acetamide (DMAC).
Described in step (1), in casting solution, each constituent mass percentage composition is preferably: SPES 20%～25%, pore former 5%～10%, remaining is solvent.
Ag [(NH described in step (3)3)2]+The mass concentration of solution is preferably 0.02%～0.08%；Described ultrafilter membrane With Ag [(NH3)2]+The mass ratio of solution is 1:(5～20).
Described in step (4), reducing agent is preferably vitamin C or glucose, the concentration of reductant solution be 0.1～ 0.5mol/L。
Preferably, dry process is washed described in step (5) as follows: respectively wash with deionized water and dehydrated alcohol successively 2～3 times, until system pH is put in vacuum drying oven after neutrality, at 50～70 DEG C, it is vacuum dried 1～3h.
Preferably, described in step (5), the mass fraction of m-diaminobenzene. aqueous solution is 0.5%～2%, and the response time is 5 ～15min；The mass fraction of the hexane solution of described pyromellitic trimethylsilyl chloride is 0.2%～1%, the response time be 5～ 15min。
A kind of antibacterial composite nanometer filtering film of loading nano silvery, is prepared by said method.
The principle of the present invention is: first with concentrated sulphuric acid, filmogen PES is carried out sulfonation, generates the sulfonation containing sulfonic acid group Polyether sulfone (SPES), by sulfonic group and Ag+Positive and negative charge interact, by Ag+Absorption is on film surface, then by reduction The reduction of agent, at film Surface Creation nanometer silver, recycling interfacial polymerization forms complex functional layer, obtains described load and receive The silver-colored antibacterial composite nanometer filtering film of rice.
Preparation method and the obtained product of the present invention have the advantage that and beneficial effect:
(1) present invention passes through charge interaction at film surface orientation loading nano silvery, it is possible to control nanometer silver at film table The distribution in face, the nanometer silver of inductive formation is uniform in film surface distributed, prevents nanometer silver agglomeration；
(2) complex functional layer can be generated by interfacial polymerization, while giving filter membrane nanofiltration ability, moreover it is possible to load Nanometer silver effectively embeds, and reduces the loss of nanometer silver；
(3) after the embedding of composite bed, the stripping quantity of nanometer silver reduces, and the time of slow release increases, NF membrane antibacterial Performance is more lasting；
(4) in the present invention, nanometer silver is embedded in inside film, affects smaller on the water flux of film with retaining characteristic；
(5) present invention prepares the antibacterial composite nanometer filtering film of loading nano silvery, and good anti-bacterial effect, for escherichia coli and golden yellow Staphylococcic antibiotic property > 96%；
(6) in the present invention, the antibacterial composite nanometer filtering film of loading nano silvery of preparation, silver addition is few, and low cost is prepared Separating film and have excellent anti-microbial property, effectively extend the service life of film, simple for process, contamination resistance is significantly Strengthen.
Accompanying drawing explanation
Fig. 1 is that the surface analysis pore volume-aperture of the embodiment of the present invention 1 antibacterial composite nanometer filtering film of gained loading nano silvery is micro- Divide scattergram；
Fig. 2 is embodiment 1 step (3) gained SPES ultrafilter membrane, step (6) gained loading nano silvery antibacterial ultrafiltration membrane and The XRD figure of the whole antibacterial composite nanometer filtering film of gained loading nano silvery；
Fig. 3 is embodiment 1 step (3) gained SPES ultrafilter membrane, step (6) gained loading nano silvery antibacterial ultrafiltration membrane and The SEM figure of the whole antibacterial composite nanometer filtering film of gained loading nano silvery；
Fig. 4 is embodiment 1 step (3) gained SPES ultrafilter membrane, step (6) gained loading nano silvery antibacterial ultrafiltration membrane and The antimicrobial absorption figure of the whole antibacterial composite nanometer filtering film of gained loading nano silvery；
Fig. 5 is embodiment 1 step (3) gained SPES ultrafilter membrane, step (6) gained loading nano silvery antibacterial ultrafiltration membrane and The whole gained loading nano silvery antibacterial composite nanometer filtering film antibacterial effect comparison diagram to different bacterium.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention do not limit In this.
Embodiment 1
(1) take 20g PES in the round-bottomed flask of 250mL, add 200mL concentrated sulphuric acid, stir 5h at 50 DEG C, solution is fallen The SPES entering to make in ice-water bath generation separates out, and washing is dried SPES；
(2) take 10g SPES and add in 37.5g DMF, stir 4h at 60 DEG C, until SPES is completely dissolved, then in solution Add 2.5g polyvinyl alcohol, at 60 DEG C, stir 2h, at 60 DEG C, stand 24h after vacuum defoamation, form casting solution；
(3) the casting solution scraper after deaeration is spread to 30um thick film on a glass, stop 10s in atmosphere, after It is immersed into film-forming in distilled water, at room temperature dries, obtain SPES ultrafilter membrane；
(4) taking above SPES ultrafilter membrane 8g, the mass fraction being immersed in 40g is 0.02% silver ion (Ag [(NH3)2]+) molten In liquid, after reaction 1h, taking-up is dried；
(5), under room temperature, the separation film above in association with silver ion is immersed in deionized water, then by (dense for 3ml vitamin C Degree is 0.1mol/L) it is added drop-wise in above-mentioned aqueous solution with the speed of 30 per minute, dropping limit, limit is slowly rocked；
(6) take out separation film, wash 3 times with deionized water, then wash 3 times with dehydrated alcohol, until system pH is close Neutral；Then sample is put in vacuum drying oven, temperature is slowly increased to 70 DEG C from 50 DEG C, be then vacuum dried at 70 DEG C 2h, i.e. can get loading nano silvery antibacterial ultrafiltration membrane；
(7) loading nano silvery antibacterial ultrafiltration membrane in (6) is the most first immersed into the m-diaminobenzene. that mass fraction is 2% In aqueous solution, reacting 10min, taking-up is dried；It is immersed into the pyromellitic trimethylsilyl chloride hexane solution that mass fraction is 0.5% again In, react 10min, taking-up is dried, and heat treatment 15min at 80 DEG C i.e. can get the antibacterial composite nanometer filtering film of loading nano silvery.
Embodiment 2
Step (1)～(3) are with embodiment 1；
(4) taking SPES ultrafilter membrane 8g, the mass fraction being immersed in 40g is 0.08% silver ion (Ag [(NH3)2]+) solution In, after reaction 1h, taking-up is dried；
(5), under room temperature, the separation film above in association with silver ion is immersed in deionized water, then by (dense for 3ml vitamin C Degree is 0.5mol/L) it is added drop-wise in above-mentioned aqueous solution with the speed of 30 per minute, dropping limit, limit is slowly rocked；
Step (6)～(7), with embodiment 1, obtain the antibacterial composite nanometer filtering film of loading nano silvery of the present embodiment.Embodiment 3
Step (1) is with embodiment 1；
(2) take 12.5g SPES and add in 33.5g DMF, stir 4h at 60 DEG C, until SPES is completely dissolved, then to solution Middle addition 4g polyvinyl alcohol, stirs 2h at 60 DEG C, stands 24h, form casting solution after vacuum defoamation at 60 DEG C；
Step (3)～(7), with embodiment 1, obtain the antibacterial composite nanometer filtering film of loading nano silvery of the present embodiment.
Embodiment 4
Step (1)～(6) are with embodiment 1；
(7) loading nano silvery antibacterial ultrafiltration membrane in (6) is the most first immersed into the isophthalic two that mass fraction is 0.5% In amine aqueous solution, reacting 2min, taking-up is dried；It is immersed into the pyromellitic trimethylsilyl chloride hexane solution that mass fraction is 0.2% again In, react 2min, taking-up is dried, and heat treatment 15min at 80 DEG C obtains the antibacterial composite nanometer filter of loading nano silvery of the present embodiment Film.
Structural characterization
Fig. 1 is that the surface analysis pore volume-aperture of the embodiment of the present invention 1 antibacterial composite nanometer filtering film of gained loading nano silvery is micro- Divide scattergram.As seen from Figure 1, within the pore-size distribution of the antibacterial composite nanometer filtering film of loading nano silvery is concentrated mainly on 5nm, may be used Several apertures are 2.091nm.By pore volume-aperture differential scattergram, the filter membrane of preparation has nanofiltration ability.
Fig. 2 is embodiment 1 step (3) gained SPES ultrafilter membrane, step (6) gained loading nano silvery antibacterial ultrafiltration membrane and The XRD figure of the whole antibacterial composite nanometer filtering film of gained loading nano silvery.As seen from Figure 2, SPES have between 22～25 ° one the widest Peak, this is the non-crystalline structure of SPES, SPES loading nano silvery antibacterial ultrafiltration membrane and the antibacterial composite nanometer filtering film of loading nano silvery Have identical peak crystallization, be both present in 38.2 °, 43.8 °, 64.7 °, at 77.2 °, these peaks and report consistent in document, be The peak crystallization of typical nanometer silver, the appearance of nanometer silver peak crystallization, represent that nanometer silver has the most successfully been supported on SPES film, Due to the embedding effect of nanofiltration layer, peak intensity has weakened.
Fig. 3 is embodiment 1 step (3) gained SPES ultrafilter membrane (a), step (6) gained loading nano silvery antibacterial ultrafiltration membrane The SEM figure of (b) and the final antibacterial composite nanometer filtering film (c) of gained loading nano silvery.As seen from Figure 3, in the visual field of 5 μm, SPES ultrafiltration membrane surface is dense, does not occur that receiving occur in obvious hole, the surface of SPES loading nano silvery antibacterial ultrafiltration membrane Rice Argent grain, nanometer silver is in granular form, it can be seen that nano-Ag particles duty factor is more uniform, the antibacterial composite nanometer filter of loading nano silvery The composite bed that film surface aggregate is fine and close, this is oil phase monomer and aqueous phase monomers reacts in interface, the fine and close merit of generation Ergosphere, this composite bed makes filter membrane have the ability of nanofiltration, and is embedded on film by nanometer silver.It can be seen that receive from SEM figure Meter Yin is supported on film, successfully defines complex functional layer on film surface by interfacial polymerization.
Anti-microbial property is tested
Test strain is escherichia coli, staphylococcus aureus and pseudomonas, uses cell adsorption method to test anti- Bacterium property.Compound concentration is 108The escherichia coli bacteria suspension of CFU/mL, 106The staphylococcus aureus of CFU/mL and pseudomonas bacterium Suspension, by embodiment 1 step (3) gained SPES ultrafilter membrane, step (6) gained loading nano silvery antibacterial ultrafiltration membrane and final gained The antibacterial composite nanometer filtering film of loading nano silvery is cut into the square that the length of side is 2cm, is immersed into 10ml each strain corresponding concentration above-mentioned Bacteria suspension in, after cultivating 2h under 250r/min, the constant-temperature table of 37 DEG C, take out diaphragm, wash 2 times with sterilized water, remove The unadsorbed microorganism on film surface.Diaphragm is immersed into ultrasonic 10min in 10mL sterilized water (power is 240W, 50kHz) again, Absorption is distributed in sterilized water in the microorganism of membrane surface, sterilized water is diluted 102Take 100 μ L after Bei and be coated on LB solid In culture medium, cultivate 12h at 37 DEG C, according to clump count on flat board, carry out the antimicrobial absorbability of characterization of membrane.Accordingly, will Take out remaining bacteria suspension after diaphragm, dilute 103Take 100 μ L after Bei to be coated on LB solid medium, at 37 DEG C, cultivate 24h, Make blank with the bacteria suspension not adding any diaphragm, calculate the microbe colony number on each culture dish, and with following Formula calculating antibiotic rate:
Antibiotic rate=(N0-N)/N0× 100%, wherein corresponding after being addition diaphragm for N clump count, N0For not adding diaphragm pair The clump count answered.
Fig. 4 is embodiment 1 step (3) gained SPES ultrafilter membrane, step (6) gained loading nano silvery antibacterial ultrafiltration membrane and Antimicrobial absorption figure (the test strain: a, d, g are escherichia coli of the whole antibacterial composite nanometer filtering film of gained loading nano silvery；B, e, h For pseudomonas；C, f, i are staphylococcus aureus；Test diaphragm: a-c is SPES ultrafilter membrane；D-f is that loading nano silvery is antibacterial Ultrafilter membrane；G-i is the antibacterial composite nanometer filtering film of loading nano silvery).As seen from Figure 4, after the absorption microorganism of SPES ultrafiltration diaphragm, Overgrowing with microorganism on corresponding culture dish, the most colibacillary quantity is slightly less than staphylococcus aureus, and SPES is described Substantial amounts of microorganism adsorption can be produced.Loading nano silvery antibacterial ultrafiltration membrane, the clump count on corresponding culture dish all less than 20, Because the existence of nanometer silver, the growth of microorganism on diaphragm, SPES@Ag can be effectively suppressed to have good antimicrobial adsorptivity Can, the antibacterial composite nanometer filtering film of loading nano silvery, a little higher than SPES of clump count of corresponding culture dish carries silver ultrafilter membrane, because warp After crossing the embedding of functional layer, the burst size of nanometer silver can reduce, and makes sterilizing ability decrease.
Fig. 5 is embodiment 1 step (3) gained SPES ultrafilter membrane (1), step (6) gained loading nano silvery antibacterial ultrafiltration membrane And the final antibacterial composite nanometer filtering film of the gained loading nano silvery (3) the antibacterial effect comparison diagram to different bacterium (2).Permissible by Fig. 5 Finding out, SPES ultrafilter membrane, for the microorganism common for three kinds, escherichia coli, pseudomonas and staphylococcus aureus, has Certain antibacterial ability, its antibiotic rate is respectively 18.7 ± 3.5%, and 29.3 ± 6.0%, 14.0 ± 5.6%, this is because SPES The sulfonic group on surface has certain antibacterial ability, and when the sulfonic group of microorganism with film surface contacts, microorganism gradually loses The biomorph that itself is complete, ultimately results in death.Loading nano silvery antibacterial ultrafiltration membrane shows the strongest antibiotic property, for upper The antibiotic rate stating three kinds of microorganisms has respectively reached 96.7 ± 1.2%, and 98.3 ± 0.6%, 87.7% ± 3.1%, nanometer silver Exist, greatly improve the antibacterial ability of film.The antibacterial composite nanometer filtering film of loading nano silvery shows good antibiotic property equally, Antibiotic rate for above-mentioned three kinds of microorganisms has respectively reached 89.0 ± 2.0%, and 89.3 ± 1.5%, 80.0% ± 3.0%, warp After crossing interfacial polymerization, the anti-microbial property of NF membrane does not significantly decrease.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify, All should be the substitute mode of equivalence, within being included in protection scope of the present invention.

Claims (8)

1. the preparation method of the antibacterial composite nanometer filtering film of loading nano silvery, it is characterised in that include following preparation process:
(1) with concentrated sulphuric acid by PES sulfonation, SPES is obtained；SPES and pore former being dissolved in a solvent, at 50～80 DEG C, stirring is mixed Close the most also deaeration, be made into casting solution；
(2) by step (1) gained casting solution knifing, then it is immersed in distilled water solidification, after drying, obtains ultrafilter membrane；
(3) load combines silver ion: step (2) gained ultrafilter membrane is immersed in Ag [(NH3)2]+In solution, take after reaction 1～2h Go out to dry；
(4) being immersed in deionized water by step (3) gained ultrafilter membrane under room temperature, then dropping reductant solution generates nanometer Silver；
(5) washing of step (4) gained ultrafilter membrane being dried, be then immersed in m-diaminobenzene. aqueous solution reaction, taking-up is dried, then It is immersed in the hexane solution of pyromellitic trimethylsilyl chloride reaction, takes out after drying heat treatment 10～15min at 50～80 DEG C, To the antibacterial composite nanometer filtering film of described loading nano silvery.
The preparation method of the antibacterial composite nanometer filtering film of a kind of loading nano silvery the most according to claim 1, it is characterised in that: step Suddenly pore former described in (1) is polyvinyl alcohol or polyvinylpyrrolidone；Described solvent is N-Methyl pyrrolidone, N, N-diformazan Base Methanamide or DMAC N,N' dimethyl acetamide.
The preparation method of the antibacterial composite nanometer filtering film of a kind of loading nano silvery the most according to claim 1, it is characterised in that: step Suddenly described in (1), in casting solution, each constituent mass percentage composition is: SPES 20%～25%, pore former 5%～10%, remaining For solvent.
The preparation method of the antibacterial composite nanometer filtering film of a kind of loading nano silvery the most according to claim 1, it is characterised in that: step Suddenly Ag [(NH described in (3)3)2]+The mass concentration of solution is 0.02%～0.08%；Described ultrafilter membrane and Ag [(NH3)2]+Molten The mass ratio of liquid is 1:(5～20).
The preparation method of the antibacterial composite nanometer filtering film of a kind of loading nano silvery the most according to claim 1, it is characterised in that: step Suddenly reducing agent described in (4) is vitamin C or glucose, and the concentration of reductant solution is 0.1～0.5mol/L.
The preparation method of the antibacterial composite nanometer filtering film of a kind of loading nano silvery the most according to claim 1, it is characterised in that step Suddenly dry process is washed described in (5) as follows: respectively wash 2～3 times with deionized water and dehydrated alcohol successively, until system pH Value is put in vacuum drying oven after neutrality, is vacuum dried 1～3h at 50～70 DEG C.
The preparation method of the antibacterial composite nanometer filtering film of a kind of loading nano silvery the most according to claim 1, it is characterised in that: step Suddenly the mass fraction of m-diaminobenzene. aqueous solution described in (5) is 0.5%～2%, and the response time is 5～15min；Described equal benzene three The mass fraction of the hexane solution of formyl chloride is 0.2%～1%, and the response time is 5～15min.
8. the antibacterial composite nanometer filtering film of loading nano silvery, it is characterised in that: by the side described in any one of claim 1～7 Method prepares.
CN201610609458.6A 2016-07-28 2016-07-28 A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof Pending CN106215724A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610609458.6A CN106215724A (en) 2016-07-28 2016-07-28 A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610609458.6A CN106215724A (en) 2016-07-28 2016-07-28 A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof

Publications (1)

Publication Number Publication Date
CN106215724A true CN106215724A (en) 2016-12-14

Family

ID=57535818

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610609458.6A Pending CN106215724A (en) 2016-07-28 2016-07-28 A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106215724A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108588289A (en) * 2018-05-17 2018-09-28 中国科学院过程工程研究所 A kind of antibiotic device, antibiotic method, embrane method cane sugar manufacture system and processing method for embrane method cane sugar manufacture system
CN112316753A (en) * 2020-09-22 2021-02-05 宁波方太厨具有限公司 Preparation method of high-flux loose hollow fiber nanofiltration membrane
CN112940333A (en) * 2021-04-29 2021-06-11 北京工商大学 Antibacterial food packaging film and preparation method thereof
CN112973473A (en) * 2021-03-08 2021-06-18 天津工业大学 Reverse osmosis composite membrane resisting biological pollution and preparation method thereof
CN113004568A (en) * 2021-04-29 2021-06-22 北京工商大学 Composite antibacterial food packaging film and preparation method thereof
CN113388146A (en) * 2021-06-04 2021-09-14 北京工商大学 Antibacterial plastic bag and preparation method thereof
CN113388145A (en) * 2021-06-04 2021-09-14 北京工商大学 Antibacterial chopping board and preparation method thereof
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
CN115155341A (en) * 2022-07-15 2022-10-11 南昌航空大学 Antibacterial composite nanofiltration membrane and preparation method thereof
CN115155340A (en) * 2022-07-15 2022-10-11 南昌航空大学 Polyamide composite nanofiltration membrane containing antibacterial interlayer and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102764599A (en) * 2012-06-29 2012-11-07 清华大学 Method for preparing nanometer material mixed matrix membrane
CN103492051A (en) * 2011-12-08 2014-01-01 Lg化学株式会社 Reverse osmosis membrane comprising silver nanowire layer, and preparation method thereof
CN105597578A (en) * 2015-12-23 2016-05-25 华南理工大学 Antibacterial separating membrane with directionally induced and loaded nano-silver and preparation method of antibacterial separating membrane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103492051A (en) * 2011-12-08 2014-01-01 Lg化学株式会社 Reverse osmosis membrane comprising silver nanowire layer, and preparation method thereof
CN102764599A (en) * 2012-06-29 2012-11-07 清华大学 Method for preparing nanometer material mixed matrix membrane
CN105597578A (en) * 2015-12-23 2016-05-25 华南理工大学 Antibacterial separating membrane with directionally induced and loaded nano-silver and preparation method of antibacterial separating membrane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XUELIAN CAO等: "Immobilization of silver nanoparticles onto sulfonated polyethersulfone membranes as antibacterial materials", 《COLLOIDS AND SURFACES B: BIOINTERFACES》 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108588289A (en) * 2018-05-17 2018-09-28 中国科学院过程工程研究所 A kind of antibiotic device, antibiotic method, embrane method cane sugar manufacture system and processing method for embrane method cane sugar manufacture system
CN112316753B (en) * 2020-09-22 2022-04-19 宁波方太厨具有限公司 Preparation method of high-flux loose hollow fiber nanofiltration membrane
CN112316753A (en) * 2020-09-22 2021-02-05 宁波方太厨具有限公司 Preparation method of high-flux loose hollow fiber nanofiltration membrane
CN112973473A (en) * 2021-03-08 2021-06-18 天津工业大学 Reverse osmosis composite membrane resisting biological pollution and preparation method thereof
CN112973473B (en) * 2021-03-08 2023-03-24 天津工业大学 Reverse osmosis composite membrane resisting biological pollution and preparation method thereof
CN112940333A (en) * 2021-04-29 2021-06-11 北京工商大学 Antibacterial food packaging film and preparation method thereof
CN113004568A (en) * 2021-04-29 2021-06-22 北京工商大学 Composite antibacterial food packaging film and preparation method thereof
CN113388145A (en) * 2021-06-04 2021-09-14 北京工商大学 Antibacterial chopping board and preparation method thereof
CN113388146A (en) * 2021-06-04 2021-09-14 北京工商大学 Antibacterial plastic bag and preparation method thereof
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
CN115155341A (en) * 2022-07-15 2022-10-11 南昌航空大学 Antibacterial composite nanofiltration membrane and preparation method thereof
CN115155340A (en) * 2022-07-15 2022-10-11 南昌航空大学 Polyamide composite nanofiltration membrane containing antibacterial interlayer and preparation method thereof
CN115155340B (en) * 2022-07-15 2024-02-02 南昌航空大学 Polyamide composite nanofiltration membrane containing antibacterial interlayer and preparation method thereof
CN115155341B (en) * 2022-07-15 2024-02-02 南昌航空大学 Antibacterial composite nanofiltration membrane and preparation method thereof

Similar Documents

Publication Publication Date Title
CN106215724A (en) A kind of antibacterial composite nanometer filtering film of loading nano silvery and preparation method thereof
Liao et al. Preparation and characterization of NaY/PVDF hybrid ultrafiltration membranes containing silver ions as antibacterial materials
CN107951902B (en) Graphene antibacterial composition and sanitary material using same
CN102489168B (en) A kind of preparation method of inorganic/organic hybridization antibacterial film
Huang et al. Modification of PES membrane with Ag–SiO2: Reduction of biofouling and improvement of filtration performance
CN104548969A (en) Method for preparing anti-pollution polysulfone porous membrane by self-assembling immobilization of metal ions
CN100402134C (en) Method for preparing polymer/montmorillnoite nano composite hydrophilic membrance
CN103055726B (en) Preparation method of low-pressure high-flux nanofiltration membrane
CN108465377A (en) A kind of preparation method of regenerated cellulose/chitosan composite antibiotic NF membrane
CN112056310B (en) DFNS (double-walled carbon nanotubes) loaded carbon quantum dot/molybdenum disulfide quantum dot as well as preparation method and application thereof
CN104012573A (en) Bentonite-loaded nano silver antibacterial agent and preparation method thereof
CN106955603B (en) Surface segregation functionalized anti-pollution polymer separation membrane and preparation method thereof
CN106823865A (en) A kind of aromatic polyamide composite reverse osmosis membrane and preparation method for being grafted carbon fluorine class material and aminoglycoside antibiotics
CN104258738A (en) Forward osmosis organic-inorganic composite membrane and preparation method thereof
CN104014256A (en) Preparation method of anti-biological-pollution PVDF (polyvinylidene fluoride) film
CN106000126B (en) Bacteriostatic film based on nano zinc oxide and preparation method and application thereof
CN112056313B (en) Method for aqueous phase synthesis of nano Cu-MOF (copper-metal organic framework) bacteriostatic agent
CN107670515A (en) A kind of high-hydrophilic inorganic-organic hybrid antibacterial ultrafiltration membrane and preparation method thereof
CN109876674A (en) A kind of preparation method of high throughput stable against biological contamination reverse osmosis membrane
CN105597578B (en) A kind of directional induction loading nano silvery antibacterial seperation film and preparation method thereof
CN107174980A (en) A kind of preparation method of cellulose lamination antibacterial ultrafiltration membrane
CN101402023A (en) Antimicrobial flat-plate separation film and method of producing the same
CN102553466A (en) Antimicrobial polysulphone flat ultrafiltration membrane and preparation method thereof
CN103657433A (en) Forward-osmosis organic-inorganic composite membrane and preparation method thereof
CN108499374A (en) PVDF composite graphites alkene filter core film and its production technology

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20161214

RJ01 Rejection of invention patent application after publication