CN107983158A - A kind of antibacterial composite nanometer filtering film and preparation method thereof - Google Patents
A kind of antibacterial composite nanometer filtering film and preparation method thereof Download PDFInfo
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- CN107983158A CN107983158A CN201610946642.XA CN201610946642A CN107983158A CN 107983158 A CN107983158 A CN 107983158A CN 201610946642 A CN201610946642 A CN 201610946642A CN 107983158 A CN107983158 A CN 107983158A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
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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
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Abstract
The present invention provides a kind of antibacterial composite nanometer filtering film, including open support film bottom and surface complexation the antimicrobial surface of antibacterial metal ions；It is prepared via a method which：Infiltration processing is carried out to bottom using the aqueous phase solution comprising aqueous phase monomers, obtains being coated with the bottom of aqueous phase monomers；Infiltration processing is carried out to the bottom for being coated with aqueous phase monomers using the oil-phase solution comprising oil phase monomer, obtains being coated with the bottom of aqueous phase monomers and oil phase monomer；The bottom for being coated with aqueous phase monomers and oil phase monomer is heat-treated, the composite nanometer filtering film with polyamide functional layer is made；Infiltration processing is carried out to the composite nanometer filtering film using the metal salt solution comprising antibacterial metal ions, to obtain the final product；Wherein described aqueous phase monomers include polyethyleneimine.Antibacterial composite nanometer filtering film of the present invention improves anti-microbial property, especially resisting microbial contamination performance on the basis of high osmosis energy is kept；Anti-microbial property is lasting at the same time, service life length, and application prospect is good.
Description
Technical field
The invention belongs to technical field of membrane, is related to a kind of composite nanometer filtering film, and in particular to a kind of antibacterial composite nanometer filtering film and
Its preparation method.
Background technology
NF membrane is also known as " loose type " reverse osmosis membrane, is that a kind of one kind of aperture between reverse osmosis membrane and ultrafiltration membrane is new
Type seperation film, since it is with how electrically charged on nano level membrane aperture, film, it is allowed to which low molecule salt is retained compared with high score by rear
The organic matter and multivalent ion of son amount, have unique separating property, the separation accuracy of higher.NF membrane is widely used at present
Water softening, drink water purifying, remove the fields such as Organic substance in water, dyestuff purification concentration, the separation of natural drug and concentration, is one
Kind has the seperation film kind using future very much.
For a long time, membrane pollution problem is the main problem that restrict composite nanometer filtering film development and progress, according to pollutant
Property can be divided into inorganic matter pollution, organic pollution, particle and colloidal sol pollution and microbial contamination, wherein microbial contamination
It is due to microorganism adsorption fouling membranes caused by film surface such as bacterium in water, fungi, clearly gets up very difficult, therefore carry
High composite nanometer filtering film antibacterial surface is one of important way for reducing film surface microbial contamination.
For a long time, people are typically employed in addition inorganic antibacterial nano-particle, surface grafting antibacterial in composite nanometer filtering film
The methods of group, surface coating antiseptic, improves the anti-microbial property of film surface.Chinese patent CN103492051B is by silver nanoparticle
Line adds in aqueous phase monomers m-phenylene diamine (MPD), then prepares polyamide/silver nanoparticle with oil phase monomer pyromellitic trimethylsilyl chloride interfacial polymerization
Line composite membrane.It is compound that Chinese patent CN101874989A prepares polyam ide TLC in polysulfone supporting layer by interfacial polymerization
Film, then adds the aqueous phase solution system of the inorganic nano-particle containing silver, copper, zinc and respective compound on this polyamide surface layer
The second layer polyamide surface layer of the standby nano-particle containing antibacterial inorganic is as antibacterial functions layer.Chinese patent CN103480284A will receive
Rice Argent grain coated on polyamide reverse osmose membrane surface obtains pollution-resistant polyamide composite membrane after being mixed with PVA solution.It is Chinese special
Sharp CN104548951A discloses a kind of high salt-stopping rate antibacterial composite nanometer filtering film and preparation method thereof, after the completion of interfacial polymerization,
The attapulgite contact preparation that film and antibiotic property chitosan quaternary ammonium salt are modified antibacterial composite nanometer filtering film has been gone out into again.Chinese patent
CN103263862A introduces the trichloro-benzenes oxygen formyl chloride of antibiotic property in the oil-phase solution of interfacial polymerization, has prepared surface band
There is the composite nanometer filtering film of antibiotic property organic group.
Although these methods can improve the antibiotic property of film surface, there is also various deficiencies, such as antibacterial
Particle is easily lost in during the use of film, the Durability of antimicrobial effect of composite nanometer filtering film is poor, and the selection of antibacterial composite nanometer filtering film is oozed
The shortcomings of permeability can be bad.
The content of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide a kind of antibacterial composite nanometer filter
Film and preparation method thereof.The present invention is during composite nanometer filtering film is prepared, by selecting polyethyleneimine (PEI) to be used as water phase
Key component in monomer, is allowed to carry out interface polymerization reaction on porous support membrane with the acyl chlorides as oil phase monomer, is made
Surface has the composite nanometer filtering film of a large amount of amino；Then by composite nanometer filtering film of the surface with a large amount of amino with certain dense
A period of time is soaked in the metal ion solution of degree, a large amount of amino of film surface can make with the complexing of metal ion in solution
Obtaining the area load of the composite nanometer filtering film has the metal ion of antibacterial functions, and then is keeping composite nanometer filtering film high osmosis
The anti-microbial property of composite nanometer filtering film, especially resisting microbial contamination performance are improved on the basis of energy；Simultaneously as metal ion
Stablize with the complexing of film surface amino so that metal ion is firmly combined with, is not easily to fall off, therefore antibacterial prepared by the present invention
The anti-microbial property of composite nanometer filtering film is lasting, service life length.
According to an aspect of the invention, there is provided a kind of antibacterial composite nanometer filtering film, including bottom and antimicrobial surface；It is described
Bottom includes open support film layer；The antimicrobial surface has the polyamide functional layer of antibacterial metal ions for surface complexation.
A preferred embodiment according to the present invention, the porous support membrane are selected from polysulfone porous support membrane, polyether sulfone
One kind in porous support membrane, sulfonated polyether sulfone porous support membrane, polyacrylonitrile porous support membrane, polypropylene porous support membrane；
The molecular cut off of the porous support membrane is 3-5 ten thousand.
A preferred embodiment according to the present invention, the mass fraction of antibacterial metal ions is in the antimicrobial surface
0.5-5%.
Some preferred embodiments according to the present invention, the antibacterial metal ions include silver particles, copper particle and zinc ion
In one or more.
A preferred embodiment according to the present invention, the method system that the polyamide functional layer uses interfacial polymerization
Standby, the aqueous phase monomers in selected interfacial polymerization process must include PEI.According to one embodiment of present invention, the polyethylene
The number-average molecular weight of imines is 1000-10 ten thousand.
Antibacterial composite nanometer filtering film according to the present invention, top layer have substantial amounts of amino, the metal ions such as it is with silver-colored, copper and zinc
Stable ligand is formed by complexing, a large amount of antibacterial metal ions are supported on the surface of composite nanometer filtering film, when bacterium,
For fungi when pollutant contacts film surface, these metal ions can pass through its internal structure of the cell membrane disruption through microorganism
Etc. the effect that mode has given play to antibacterial so that the anti-microbial property of composite nanometer filtering film improves a lot；And due to film surface complexing
Metal ion is minimum, is only that angstrom level is other, will not destroy the internal structure of polyamide functional layer, therefore will not be to composite nanometer filtering film
Water flux and salt-stopping rate adversely affect；Complexing is stablized at the same time so that film surface anti-microbial property persistence is good, prolongs significantly
The service life of composite nanometer filtering film is grown.
According to another aspect of the present invention, there is provided a kind of preparation method of antibacterial composite nanometer filtering film, includes the following steps：
S1. infiltration processing is carried out to bottom using the aqueous phase solution comprising aqueous phase monomers, obtains being coated with aqueous phase monomers
Bottom；Wherein described aqueous phase monomers include polyethyleneimine；
S2. infiltration processing is carried out to the bottom for being coated with aqueous phase monomers using the oil-phase solution comprising oil phase monomer,
Obtain being coated with the bottom of aqueous phase monomers and oil phase monomer；
S3. the bottom for being coated with aqueous phase monomers and oil phase monomer is heat-treated, being made has polyamides amine functions
The composite nanometer filtering film of layer；
S4. infiltration processing is carried out to the composite nanometer filtering film using the metal salt solution comprising antibacterial metal ions, be made
Antibacterial composite nanometer filtering film with antimicrobial surface.
Preparation in accordance with the present invention, the mass fraction of antibacterial metal ions is 0.5-5% in the antimicrobial surface.
Some preferred embodiments according to the present invention, the antibacterial metal ions include silver particles, copper particle and zinc ion
In one or more.
According to one embodiment of present invention, the number-average molecular weight of the polyethyleneimine is 1000-10 ten thousand.The poly- second
Contain substantial amounts of amino in alkene imines strand so that on the composite membrane of formation, there are a large amount of amino can be with metal ion network
Close, make being incorporated on composite nanometer filtering film for metal ion stabilization, improve the Durability of antimicrobial effect of composite nanometer filtering film.
A preferred embodiment according to the present invention, the bottom include open support film layer.It is specific real at some
Apply in example, the porous support membrane is selected from polysulfone porous support membrane, polyether sulfone porous support membrane, sulfonated polyether sulfone open support
One kind in film, polyacrylonitrile porous support membrane, polypropylene porous support membrane；The molecular cut off of the porous support membrane is 3-
50000.
Preparation in accordance with the present invention, there is no particular limitation for the method handled for the infiltration in step S1, according to
The existing method of this area.For example, when bottom to be carried out in the aqueous phase solution comprising aqueous phase monomers to one section of infiltration processing
Between, then remove unnecessary aqueous phase solution, to obtain the final product.
In some embodiments of the invention, in step sl, it is described that infiltration processing is carried out to bottom using aqueous phase solution
Time be 5-30s, be preferably 10-15s.
According to some embodiments of the present invention, the aqueous phase monomers further include in addition to polyethyleneimine containing two or
The compound of two or more reactive amino.The compound containing two or more reactive aminos includes isophthalic two
One or more in amine, o-phenylenediamine, p-phenylenediamine, ethylenediamine, piperazine and 4- aminomethylpiperazines.
A preferred embodiment according to the present invention, the concentration of aqueous phase monomers is 1-30g/L in the aqueous phase solution.
In some embodiments of the present invention, the percentage that the quality of the polyethyleneimine accounts for the aqueous phase monomers gross mass is 70%-
100%, it is preferably 80%-100%.
Preparation in accordance with the present invention, there is no particular limitation for the method handled for the infiltration in step S2, according to
The existing method of this area.For example, will be coated with the bottoms of aqueous phase monomers in the oil-phase solution comprising oil phase monomer into
Row infiltration processing a period of time, then remove unnecessary oil-phase solution, to obtain the final product.
In some embodiments of the invention, in step s 2, the time of the infiltration processing is 5-30s, is preferably 10-
15s。
A preferred embodiment according to the present invention, the oil phase monomer include containing two or more acid chloride groups
Chloride compounds.Preferably, the oil phase monomer includes pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, m-phthaloyl chloride, adjacent benzene
One or more in three acyl chlorides of dimethyl chloride, three acyl chlorides of fourth and cyclopropane.
Process in accordance with the present invention S2, for the solvent in the oil-phase solution, there is no particular limitation, selects this area
Common organic solvent.Preferably, the solvent includes n-hexane, hexamethylene, normal octane, toluene, ethylbenzene, ISOPAR E
One or more in solvent naphtha and ISOPAR G solvent oil.
According to a preferred embodiment of the present invention, the concentration of oil phase monomer is 0.5-5g/L in the oil-phase solution.
Preparation in accordance with the present invention, includes for the heat-treating methods in step S3：Water phase is coated with to described
The bottom of monomer and oil phase monomer is dried, is heat-treated, and the interfacial polymerization of aqueous phase monomers and oil phase monomer is further completed,
The composite nanometer filtering film with polyamide functional layer is made.
According to some embodiments of the present invention, the temperature of the heat treatment is 30-120 DEG C, is preferably 50-100 DEG C；It is described
The time of heat treatment is 1-10min, is preferably 3-6min.
Preparation in accordance with the present invention, the polyamide work(for having antibacterial metal ions with surface complexation is made in step S4
The antibacterial composite nanometer filtering film of ergosphere, including：Composite nanometer filtering film made from step S3 is placed in the solution comprising antibacterial metal ions
In carry out infiltration processing, take out, washing, to obtain the final product.
A preferred embodiment according to the present invention, the time that processing is infiltrated described in step S4 are 2-30h, are preferably
10-20h。
S4 according to the present invention, for the washing, there is no particular limitation.It is for instance possible to use deionized water is to infiltration
Composite nanometer filtering film afterwards rinses, until the metal ion of composite nanometer filtering film excess surface is rinsed well.
A preferred embodiment according to the present invention, the metal salt solution comprising antibacterial metal ions are to include silver
The metal salt solution of ion and/or copper ion and/or zinc ion；Preferably, the metal salt includes silver nitrate, copper chloride, sulphur
One or more in sour copper, copper nitrate, copper acetate, zinc chloride, zinc acetate and zinc nitrate.
According to a preferred embodiment of the present invention, the mass fraction of the metal salt solution is 1-15%, in the present invention
Some specific embodiments in, the mass fraction of the metal salt solution is preferably 5-15%.
According to another aspect of the present invention, there is provided a kind of above-mentioned antibacterial composite nanometer filtering film is prepared according to the method described above
Application of the antibacterial composite nanometer filtering film in permeability and separation.
The present invention selects polyethyleneimine or its mixture to be used as aqueous phase monomers, and polyethyleneimine is with can largely react
Amino, is allowed to carry out interface polymerization reaction on porous support membrane with the acyl chlorides as oil phase monomer first, obtained surface has
The composite nanometer filtering film of a large amount of amino；Then by the surface have a large amount of amino composite nanometer filtering film with antibacterial metal ions network
Close, there are substantial amounts of antibacterial metal ions in the surface complexation of composite nanometer filtering film, make the composite membrane keep composite nanometer filtering film high
The anti-microbial property of composite nanometer filtering film, especially resisting microbial contamination performance are improved on the basis of permeance property；Also, due to gold
The complexing for belonging to ion and film surface amino is stablized so that metal ion is firmly combined with, is not easily to fall off, therefore prepared by the present invention
Antibacterial composite nanometer filtering film anti-microbial property it is lasting, service life length.The preparation method of antibacterial composite nanometer filtering film of the present invention is simple
Easy, the antibacterial composite nanometer filtering film of preparation has the antibiotic property of broad spectrum durable, while the permselective property of antibacterial composite nanometer filtering film
Can be good.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, these embodiments only serve illustrative, do not limit to
In the application range of the present invention.
The present invention antibacterial utilized thin film composite membranes performance evaluation and evaluation method is as follows：
(1) separating property is evaluated：
Salt-stopping rate R is defined as：Under the conditions of certain operating pressure, feeding liquid salinity (Cf) with penetrating fluid in salinity
(Cp) difference, then divided by feeding liquid salinity.
Water flux is defined as：Under certain operating conditions, the volume of the water of per membrane area is passed through in the unit interval, its
Unit is L/ (m2·h)。
The test operation condition that antibacterial composite nanometer filtering film uses in the present invention for：Feed liquor is the aqueous sodium sulfate of 1000ppm
Liquid, operating pressure 0.6MPa, operation temperature are 25 DEG C, pH value of water solution 7.0.
(2) antibacterial effect quantitatively detects：
100-2004 testing standard of the antibacterial examination criteria with reference to Textiles in USA chemistry printing and dyeing association (AATCC).Will be anti-
Bacterium composite nanometer filtering film cuts into the sample of 40mm × 40mm, by Escherichia coli (ATCC 25922) bacterium of above-mentioned sample and 100 μ L
Liquid contacts, and 30-120min is cultivated in 37 DEG C of constant incubator, and then rinses sample repeatedly with 10mL PBS buffer, takes
Progress viable bacteria culture counts after washing lotion makees appropriate dilution.Common composite nanometer filtering film (not containing antimicrobial component) is contrasted at the same time
Experiment.Sterilizing rate calculates as follows：
Sterilizing rate (%)=((A-B)/A) × 100 (formula 2)
In formula：A-common composite nanometer filter membrane sample viable count；
B-antibacterial composite nanometer filter membrane sample viable count.
(3) content detection of antibacterial metal ions：
Using the Apollo XP types X-ray energy spectrometers (EDS) of EDAX companies of U.S. production to prepared antibacterial composite nanometer filter
Film surface is characterized, and is obtained mass fraction of the antibacterial metal ions in antibacterial composite nanometer filtering film top layer, is needed in test process
The resolution ratio for ensureing energy disperse spectroscopy is 131eV.
Embodiment 1
The aqueous phase solution that aqueous phase monomers concentration is 5g/L is prepared, wherein, aqueous phase monomers are PEI and piperazine, and it is mutually single that PEI accounts for water
The number-average molecular weight that the percentage of body gross mass is 70%, PEI is 2000；It is more using the polyether sulfone that molecular cut off is 3-5 ten thousand
Hole support membrane, is placed in infiltration processing 10s in aqueous phase solution, outwells unnecessary aqueous phase solution, be made and be coated with the more of aqueous phase monomers
Hole support membrane, is then done film surface roller with clean rubber rollers；The porous support membrane for being coated with aqueous phase monomers is placed in concentration
For infiltration processing 10s in the ISOPAR E petroleum spirits of the pyromellitic trimethylsilyl chloride of 1g/L, unnecessary oil-phase solution is outwelled, then
Dry in atmosphere, be subsequently placed in 70 DEG C of drying in oven processing 1.5min, composite nanometer filtering film is obtained after taking-up；Prepare quality point
Number is 5% copper sulfate solution, and composite nanometer filtering film is placed in the solution after immersion treatment 3h and is taken out, with deionized water repeatedly
Film surface is rinsed to remove unnecessary copper sulphate, obtains antibacterial composite nanometer filtering film, the antibacterial composite nanometer filtering film prepared is stored in
In deionized water；By the test method of the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal ions content
Prepared Nano filtering composite membrane is tested and characterized, the test result of gained is listed in table 1.
Embodiment 2
The number-average molecular weight that the mass percent that the present embodiment removes PEI in aqueous phase monomers is 80%, PEI is outside 5000,
It is same as Example 1 that remaining prepares the step of antibacterial composite nanometer filtering film.By the separating property of foregoing composite nanometer filtering film, anti-microbial property
And the test method of antibacterial metal ions content is tested and characterized to prepared Nano filtering composite membrane, the test knot of gained
Fruit is listed in table 1.
Embodiment 3
The number-average molecular weight that the mass percent that the present embodiment removes PEI in aqueous phase monomers is 90%, PEI is outside 10000,
It is same as Example 1 that remaining prepares the step of antibacterial composite nanometer filtering film.By the separating property of foregoing composite nanometer filtering film, anti-microbial property
And the test method of antibacterial metal ions content is tested and characterized to prepared Nano filtering composite membrane, the test knot of gained
Fruit is listed in table 1.
Embodiment 4
In addition to aqueous phase monomers all replace with the PEI that number-average molecular weight is 30000, remaining prepares antibacterial and answers the present embodiment
The step of closing NF membrane is same as Example 1.By the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal from
The test method of sub- content is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table 1.
Comparative example 1
This comparative example is outside 30000 except the number-average molecular weight that the mass percent of aqueous phase monomers PEI is 80%, PEI, its
The step of remaining preparation antibacterial composite nanometer filtering film, is same as Example 1.By the separating property of foregoing composite nanometer filtering film, anti-microbial property with
And the test method of antibacterial metal ions content is tested and characterized to prepared Nano filtering composite membrane, the test result of gained
It is listed in table 1.
Comparative example 2
This comparative example by aqueous phase solution in addition to the piperazine solution of 5g/L is replaced with, the step of remaining prepares composite nanometer filtering film
It is same as Example 1.By the test side of the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal ions content
Method is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table 1.
Embodiment 5
The aqueous phase solution that aqueous phase monomers concentration is 7.5g/L is prepared, wherein aqueous phase monomers include PEI and piperazine, the matter of PEI
It is 60000 to measure the number-average molecular weight that percentage is 80%, PEI；Polysulfone porous support membrane using molecular cut off for 3-5 ten thousand,
Infiltration processing 30s, outwells unnecessary aqueous phase solution in aqueous phase solution, the porous support membrane for being coated with aqueous phase monomers is made, so
Film surface roller is done with clean rubber rollers afterwards；Compound concentration is the pyromellitic trimethylsilyl chloride hexane solution of 1g/L；By obtained painting
The porous support membrane for having covered aqueous phase monomers is placed in infiltration processing 30s in oil-phase solution, unnecessary oil-phase solution is outwelled, then in sky
Dried in gas, film is then placed in 45 DEG C of drying in oven processing 5min, composite nanometer filtering film is obtained after taking-up；Prepare mass fraction
For 10% aqueous zinc acetate solution, composite nanometer filtering film is placed in the solution after immersion treatment 2h and is taken out, with deionized water repeatedly
Film surface is rinsed to remove unnecessary zinc acetate, obtains antibacterial composite nanometer filtering film, the antibacterial composite nanometer filtering film prepared is stored in
In deionized water；By the test method of the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal ions content
Prepared Nano filtering composite membrane is tested and characterized, the test result of gained is listed in table 2.
Embodiment 6
Immersion treatment time of the composite nanometer filtering film in aqueous zinc acetate solution in addition to 5h is replaced with by the present embodiment, remaining system
The step of standby composite nanometer filtering film, is same as Example 5.By the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial gold
The test method for belonging to ion concentration is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table 2.
Embodiment 7
The present embodiment in addition to immersion treatment time of the composite nanometer filtering film in aqueous zinc acetate solution is replaced with 10h, remaining
The step of preparing composite nanometer filtering film is same as Example 5.By the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial
The test method of metal ion content is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table
2。
Embodiment 8
The present embodiment in addition to immersion treatment time of the composite nanometer filtering film in aqueous zinc acetate solution is replaced with 20h, remaining
The step of preparing composite nanometer filtering film is same as Example 5.By the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial
The test method of metal ion content is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table
2。
Embodiment 9
The present embodiment in addition to immersion treatment time of the composite nanometer filtering film in zinc acetate aqueous solution is replaced with 30h, remaining
The step of preparing composite nanometer filtering film is same as Example 5.By the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial
The test method of metal ion content is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table
2。
Comparative example 3
In addition to aqueous zinc acetate solution immersion treatment film is not had to after the completion of interfacial polymerization, remaining prepares compound this comparative example
The step of NF membrane, is same as Example 5.By the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal ions
The test method of content is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table 2.
Comparative example 4
In addition to immersion treatment time of the film in aqueous zinc acetate solution is replaced with 0.5h, remaining prepares compound this comparative example
The step of NF membrane, is same as Example 5.By the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal ions
The test method of content is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table 2.
Embodiment 10
The aqueous phase solution that aqueous phase monomers concentration is 10g/L is prepared, wherein aqueous phase monomers are PEI, its number-average molecular weight is 10
Ten thousand；Using the sulfonated polyether sulfone porous support membrane that molecular cut off is 50,000, infiltration processing 60s in aqueous phase solution is placed in, is outwelled more
Remaining aqueous phase solution, is made the porous support membrane for being coated with aqueous phase monomers, is then done film surface roller with clean rubber rollers；Prepare
The pyromellitic trimethylsilyl chloride ISOPAR G solvent oil solutions of 1g/L；By film and oil-phase solution infiltration processing 60s, unnecessary oil phase is outwelled
Solution, then dries in atmosphere, and film then is placed in 90 DEG C of drying in oven processing 1min, composite nanometer filter is obtained after taking-up
Film；The silver nitrate aqueous solution that mass fraction is 1% is prepared, composite nanometer filtering film is placed in the solution after immersion treatment 5h and is taken out,
Film surface is rinsed repeatedly with deionized water to remove unnecessary silver nitrate, obtains antibacterial composite nanometer filtering film, the antibacterial prepared is answered
NF membrane is closed to preserve in deionized water.By the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal ions
The test method of content is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table 3.
Embodiment 11
The present embodiment in addition to the mass fraction of silver nitrate solution is replaced 5%, the step of remaining prepares composite nanometer filtering film with
Embodiment 10 is identical.By the test side of the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal ions content
Method is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table 3.
Embodiment 12
The present embodiment in addition to the mass fraction of silver nitrate solution is replaced 10%, the step of remaining prepares composite nanometer filtering film with
Embodiment 10 is identical.By the test side of the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal ions content
Method is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table 3.
Embodiment 13
Silver nitrate solution mass fraction in addition to being replaced 15% by this comparative example, the step of remaining prepares composite nanometer filtering film and reality
It is identical to apply example 10.By the test method of the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal ions content
Prepared Nano filtering composite membrane is tested and characterized, the test result of gained is listed in table 3.
Comparative example 5
The mass fraction of silver nitrate solution in addition to being replaced 0.5% by this comparative example, the step of remaining prepares composite nanometer filtering film
It is same as in Example 10.By the test of the separating property of foregoing composite nanometer filtering film, anti-microbial property and antibacterial metal ions content
Method is tested and characterized to prepared Nano filtering composite membrane, and the test result of gained is listed in table 3.
Embodiment 14
The antibacterial composite nanometer filter membrane preparation method of the present embodiment is same as Example 1, according to the anti-of foregoing composite nanometer filtering film
The test method of bacterium performance and antibacterial metal ions content is tested and characterized to prepared Nano filtering composite membrane, is obtained
Test result is denoted as sterilizing rate -1 and film surface antibacterial metal ions quality -1；The antibacterial composite nanometer filtering film prepared is soaked in
Taken out in deionized water after 90 days, the test of anti-microbial property and antibacterial metal ions content according still further to foregoing composite nanometer filtering film
Method is tested and characterized to prepared Nano filtering composite membrane, and obtained test result is denoted as sterilizing rate -2 and film surface antibacterial
Metal ion mass fraction -2, the test result of gained are listed in table 4.
Embodiment 15
The antibacterial composite nanometer filter membrane preparation method of the present embodiment is same as Example 5, according to the anti-of foregoing composite nanometer filtering film
The test method of bacterium performance and antibacterial metal ions content is tested and characterized to prepared Nano filtering composite membrane, is obtained
Test result is denoted as sterilizing rate -1 and film surface antibacterial metal ions mass fraction -1；The antibacterial composite nanometer filtering film prepared is soaked
Steep and taken out in deionized water after 90 days, the anti-microbial property and antibacterial metal ions content according still further to foregoing composite nanometer filtering film
Test method is tested and characterized to prepared Nano filtering composite membrane, and obtained test result is denoted as sterilizing rate -2 and film surface
Antibacterial metal ions mass fraction -2, the test result of gained are listed in table 4.
Embodiment 16
The antibacterial composite nanometer filter membrane preparation method of the present embodiment is same as in Example 10, according to the anti-of foregoing composite nanometer filtering film
The test method of bacterium performance and antibacterial metal ions content is tested and characterized to prepared Nano filtering composite membrane, is obtained
Test result is denoted as sterilizing rate -1 and film surface antibacterial metal ions mass fraction -1；The antibacterial composite nanometer filtering film prepared is soaked
Steep and taken out in deionized water after 90 days, the anti-microbial property and antibacterial metal ions content according still further to foregoing composite nanometer filtering film
Test method is tested and characterized to prepared Nano filtering composite membrane, and obtained test result is denoted as sterilizing rate -2 and film surface
Antibacterial metal ions mass fraction -2, the test result of gained are listed in table 4.
Comparative example 6
The aqueous phase solution that aqueous phase monomers concentration is 5g/L is prepared, wherein, aqueous phase monomers are piperazine；It is using molecular cut off
The polyether sulfone porous support membrane of 3-5 ten thousand, is placed in infiltration processing 10s in aqueous phase solution, outwells unnecessary aqueous phase solution, coating is made
The porous support membrane of aqueous phase monomers, is then done film surface roller with clean rubber rollers；The porous of aqueous phase monomers will be coated with
Support membrane is placed in infiltration processing 10s in the ISOPAR E petroleum spirits for the pyromellitic trimethylsilyl chloride that concentration is 1g/L, and it is unnecessary to outwell
Oil-phase solution, then dry in atmosphere, be subsequently placed in 70 DEG C of drying in oven processing 1.5min, compound receive is obtained after taking-up
Filter membrane；The nano silver particles aqueous solution that mass fraction is 10% is prepared, composite nanometer filtering film is placed in immersion treatment 2h in the solution
After take out, obtain antibacterial composite nanometer filtering film, the antibacterial composite nanometer filtering film for preparing preserves in deionized water；Compound received by foregoing
The test method of the anti-microbial property of filter membrane is tested and characterized to prepared Nano filtering composite membrane, and obtained test result is denoted as
Sterilizing rate -1；The antibacterial composite nanometer filtering film prepared was soaked in deionized water after 90 days and is taken out, compound is received according still further to foregoing
The test method of the anti-microbial property of filter membrane is tested and characterized to prepared Nano filtering composite membrane, and obtained test result is denoted as
Sterilizing rate -2, the test result of gained are listed in table 4.
Comparative example 7
This comparative example is removed replaces with the shell that mass fraction is 10% the nano silver particles aqueous solution that mass fraction is 10%
After glycan is quaternary ammonium salt-modified outside attapulgite aqueous solution, the step of remaining prepares composite nanometer filtering film, is identical with comparative example 6.By foregoing
The test method of the anti-microbial property of composite nanometer filtering film is tested and characterized to prepared Nano filtering composite membrane, obtained test knot
Fruit is denoted as sterilizing rate -1；The antibacterial composite nanometer filtering film prepared was soaked in deionized water after 90 days and is taken out, according still further to foregoing
The test method of the anti-microbial property of composite nanometer filtering film is tested and characterized to prepared Nano filtering composite membrane, obtained test knot
Fruit is denoted as sterilizing rate -2, and the test result of gained is listed in table 4.
Table 1
As can be seen that the species and ratio of adjustment aqueous phase monomers from the data of the embodiment 1-4 and comparative example 1-2 of table 1
Example can obtain the antibacterial composite nanometer filtering film with different permselective properties energy, with the increasing of PEI proportions in aqueous phase monomers
Add, the salt-stopping rate of antibacterial composite nanometer filtering film improves successively.And as PEI in aqueous phase monomers it can be seen from the data of sterilizing rate
When mass percent is 70%-100%, the antibacterial metal ions concentration of antibacterial composite nanometer filtering film surface complexation is high, sterilizing rate
It is higher；And when the mass percent of PEI is less than this scope, the antibacterial metal ions concentration of antibacterial composite nanometer filtering film surface complexation
Substantially reduced with sterilizing rate, the salt-stopping rate of antibacterial composite nanometer filtering film has also declined；And if be added without in aqueous phase monomers
PEI, the surface of antibacterial composite nanometer filtering film cannot then be complexed antibacterial metal ions, also without bactericidal effect.
Table 2
As can be seen that being received using metal ion solution to compound from the data of the embodiment 5-9 and comparative example 3-4 of table 2
Filter membrane, which carries out infiltration processing, can't influence the permselective property energy of composite nanometer filtering film；When the species and concentration of metal ion are constant
When, in the range of the processing time of the present invention, processing time is longer, and the metal ion mass fraction of composite nanometer filter film surface is got over
Height, the sterilizing rate of film are also higher；Do not process or composite nanometer filtering film (comparative example 3, comparative example 4) that processing time is too short,
There is no obvious antibacterial effect；Between when treated >=30h (embodiment 9), the metal ion mass fraction and sterilizing rate of film surface
Unobvious are improved, illustrate that film surface complexation of metal ions reaches saturation.
Table 3
As can be seen that being handled in species of metal ion and infiltration from the data of the embodiment 10-13 of table 3 and comparative example 6
In the case that time is constant, the mass fraction of metal ion solution is higher, the metal ion mass fraction of film surface complexing load
Higher, sterilizing rate is higher；And the composite nanometer filtering film top layer antibacterial prepared by metal ion solution mass fraction too low (comparative example 6)
Metal ion mass fraction is not high, without too obvious antibacterial effect；(implement when metal ion solution mass fraction >=15%
Example 13), film surface complexing load metal ion mass fraction and sterilizing rate improve unobvious, illustrate film surface complexing metal from
Son reaches saturation.
Table 4
The antibacterial that the data of embodiment 14-16 and comparative example 6,7 from table 4 can be seen that the preparation of comparative example 6,7 compound is received
Filter membrane Durability of antimicrobial effect is poor, and sterilizing rate reduces 88.7% and 92.3% respectively after soaking 90 days in deionized water；This may
It is due in comparative example 6,7, the antiseptic (attapulgite that nano silver particles, chitosan quaternary ammonium salt are modified) in film top layer exists
Combination in functional layer is insecure, after the immersion of through a long time (90 days), easily departs from from film functional layer.And use the application
After antibacterial composite nanometer filtering film prepared by method soaks 90 days in deionized water, sterilizing rate declines less, still possesses good
Antibiotic property, therefore the application antibacterial composite nanometer filtering film possesses excellent Durability of antimicrobial effect.
Any numerical value mentioned in the present invention, if simply having two between any minimum and any of the highest value
The interval of unit, then include all values of one unit of each increase from minimum to peak.For example, if statement is a kind of
The amount of component, or the value of the state-variable such as temperature, pressure, time is 50-90, it is in the present specification it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1st, 0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
Formula, all possible combinations of the numerical value between cited minimum and peak are considered to disclose.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (11)
1. a kind of antibacterial composite nanometer filtering film, including bottom and antimicrobial surface；The bottom includes open support film layer；The antibacterial
Top layer has the polyamide functional layer of antibacterial metal ions for surface complexation.
2. antibacterial composite nanometer filtering film according to claim 1, it is characterised in that antibacterial metal ions in the antimicrobial surface
Mass fraction be 0.5-5%.
3. antibacterial composite nanometer filtering film according to claim 1 or 2, it is characterised in that the antibacterial metal ions include silver
One or more in particle, copper particle and zinc ion.
4. a kind of preparation method of the antibacterial composite nanometer filtering film in 1-3 such as claim as described in any one, includes the following steps：
S1. infiltration processing is carried out to bottom using the aqueous phase solution comprising aqueous phase monomers, obtains being coated with the bottom of aqueous phase monomers；
Wherein described aqueous phase monomers include polyethyleneimine；
S2. infiltration processing is carried out to the bottom for being coated with aqueous phase monomers using the oil-phase solution comprising oil phase monomer, obtained
It is coated with the bottom of aqueous phase monomers and oil phase monomer；
S3. the bottom for being coated with aqueous phase monomers and oil phase monomer is heat-treated, be made with polyamide functional layer
Composite nanometer filtering film；
S4. infiltration processing is carried out to the composite nanometer filtering film using the metal salt solution comprising antibacterial metal ions, being made has
The antibacterial composite nanometer filtering film of antimicrobial surface.
5. preparation method according to claim 4, it is characterised in that the quality of antibacterial metal ions in the antimicrobial surface
Fraction is 0.5-5%；And/or the antibacterial metal ions include the one or more in silver particles, copper particle and zinc ion.
6. preparation method according to claim 4 or 5, it is characterised in that in step S1, water is mutually single in the aqueous phase solution
The concentration of body is 1-30g/L；And/or it is described use aqueous phase solution to bottom infiltration processing time for 5-30s, preferably 10-
15s。
7. according to the preparation method described in any one in claim 4-6, it is characterised in that in step S1, the water is mutually single
Body further includes the compound containing two or more reactive aminos in addition to polyethyleneimine；It is described containing two or
The compound of two or more reactive amino preferably includes m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, ethylenediamine, piperazine and 4-
One or more in aminomethylpiperazine；It is preferred that the quality of the polyethyleneimine accounts for the percentage of the aqueous phase monomers gross mass
Than for 70%-100%, more preferably 80%-100%.
8. according to the preparation method described in any one in claim 4-7, it is characterised in that described using oil in step S2
The time that phase solution carries out infiltration processing is 5-30s, is preferably 10-15s；And/or in the oil-phase solution oil phase monomer it is dense
Spend for 0.5-5g/L；And/or the oil phase monomer includes the chloride compounds containing two or more acid chloride groups, preferably wraps
Include pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, m-phthaloyl chloride, three acyl chlorides of o-phthaloyl chloride, three acyl chlorides of fourth and cyclopropane
In one or more.
9. according to the preparation method described in any one in claim 4-8, it is characterised in that be heat-treated described in step S3
Temperature is 30-120 DEG C, is preferably 50-100 DEG C, and the time of the heat treatment is 1-10min, is preferably 3-6min；And/or step
The time that processing is infiltrated described in rapid S4 is 2-30h, is preferably 10-30h.
10. according to the preparation method described in any one in claim 4-9, it is characterised in that metal salt described in step S4
Including the one or more in silver nitrate, copper chloride, copper sulphate, copper nitrate, copper acetate, zinc chloride, zinc acetate and zinc nitrate；
It is preferably 5-10% and/or the mass fraction of the metal salt solution is 1-15%.
11. one kind as described in any one in claim 1-3 antibacterial composite nanometer filtering film or according in claim 4-10 arbitrarily
The application of antibacterial composite nanometer filtering film prepared by one the method in permeability and separation.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876681A (en) * | 2019-03-14 | 2019-06-14 | 浙江工业大学 | A kind of high throughput mixed-matrix nanofiltration membrane and preparation method thereof |
| CN110433667A (en) * | 2019-09-02 | 2019-11-12 | 天津大学 | Antipollution ant-scaling seperation film and preparation method thereof |
| CN112516811A (en) * | 2019-09-17 | 2021-03-19 | 中国石油化工股份有限公司 | Silver-containing antibacterial thin-layer composite membrane and preparation method and application thereof |
| CN112516812A (en) * | 2019-09-17 | 2021-03-19 | 中国石油化工股份有限公司 | Copper-containing antibacterial thin-layer composite film and preparation method and application thereof |
| CN113634135A (en) * | 2021-08-30 | 2021-11-12 | 北京赛诺膜技术有限公司 | Hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN114618319A (en) * | 2022-03-15 | 2022-06-14 | 常州大学 | PVDF film with long-term antibacterial and anti-pollution performance and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010110624A2 (en) * | 2009-03-27 | 2010-09-30 | Bioneer Corporation | Nanoporous films and method for manufacturing the same |
| CN102112214A (en) * | 2008-08-05 | 2011-06-29 | 聚合物华润有限公司 | Functionalized thin film polyamide membranes |
| US20120226258A1 (en) * | 2009-08-07 | 2012-09-06 | Veit Otto | Device and method for eliminating biologically harmful substances from bodily fluids |
| CN103889562A (en) * | 2011-05-27 | 2014-06-25 | 康奈尔大学 | Nanoparticle-functionalized membranes, methods of making same, and uses of same |
| CN104437111A (en) * | 2014-12-16 | 2015-03-25 | 彭博 | Anti-pollution polyamide composite membrane and preparation method thereof |
| CN104548969A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing anti-pollution polysulfone porous membrane by self-assembling immobilization of metal ions |
| US20150343387A1 (en) * | 2014-05-29 | 2015-12-03 | Lg Electronics Inc. | Membranes having antibiotic and hydrophilic properties and preparation method thereof |
| CN105251372A (en) * | 2015-07-13 | 2016-01-20 | 淮海工学院 | Preparation method of anti-pollution chlorine-resistant aromatic polyamide composite membrane |
-
2016
- 2016-10-26 CN CN201610946642.XA patent/CN107983158B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112214A (en) * | 2008-08-05 | 2011-06-29 | 聚合物华润有限公司 | Functionalized thin film polyamide membranes |
| WO2010110624A2 (en) * | 2009-03-27 | 2010-09-30 | Bioneer Corporation | Nanoporous films and method for manufacturing the same |
| US20120226258A1 (en) * | 2009-08-07 | 2012-09-06 | Veit Otto | Device and method for eliminating biologically harmful substances from bodily fluids |
| CN103889562A (en) * | 2011-05-27 | 2014-06-25 | 康奈尔大学 | Nanoparticle-functionalized membranes, methods of making same, and uses of same |
| CN104548969A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing anti-pollution polysulfone porous membrane by self-assembling immobilization of metal ions |
| US20150343387A1 (en) * | 2014-05-29 | 2015-12-03 | Lg Electronics Inc. | Membranes having antibiotic and hydrophilic properties and preparation method thereof |
| CN104437111A (en) * | 2014-12-16 | 2015-03-25 | 彭博 | Anti-pollution polyamide composite membrane and preparation method thereof |
| CN105251372A (en) * | 2015-07-13 | 2016-01-20 | 淮海工学院 | Preparation method of anti-pollution chlorine-resistant aromatic polyamide composite membrane |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876681A (en) * | 2019-03-14 | 2019-06-14 | 浙江工业大学 | A kind of high throughput mixed-matrix nanofiltration membrane and preparation method thereof |
| CN109876681B (en) * | 2019-03-14 | 2021-12-14 | 浙江工业大学 | High-flux mixed matrix nanofiltration membrane and preparation method thereof |
| CN110433667A (en) * | 2019-09-02 | 2019-11-12 | 天津大学 | Antipollution ant-scaling seperation film and preparation method thereof |
| CN112516811A (en) * | 2019-09-17 | 2021-03-19 | 中国石油化工股份有限公司 | Silver-containing antibacterial thin-layer composite membrane and preparation method and application thereof |
| CN112516812A (en) * | 2019-09-17 | 2021-03-19 | 中国石油化工股份有限公司 | Copper-containing antibacterial thin-layer composite film and preparation method and application thereof |
| CN113634135A (en) * | 2021-08-30 | 2021-11-12 | 北京赛诺膜技术有限公司 | Hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN114618319A (en) * | 2022-03-15 | 2022-06-14 | 常州大学 | PVDF film with long-term antibacterial and anti-pollution performance and preparation method thereof |
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