CN105289339B - A kind of antibacterial ultrafiltration membrane and preparation method thereof and film renovation process - Google Patents
A kind of antibacterial ultrafiltration membrane and preparation method thereof and film renovation process Download PDFInfo
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- CN105289339B CN105289339B CN201510783084.5A CN201510783084A CN105289339B CN 105289339 B CN105289339 B CN 105289339B CN 201510783084 A CN201510783084 A CN 201510783084A CN 105289339 B CN105289339 B CN 105289339B
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Abstract
The invention provides a kind of antibacterial ultrafiltration membrane and preparation method thereof and film renovation process, the antibacterial ultrafiltration membrane is prepared by the ultrafiltration membrane material with the repeat unit shown in Formulas I or Formula II, N Cl keys are included in repeat unit shown in the Formulas I or Formula II, make antibacterial ultrafiltration membrane prepared by the ultrafiltration membrane material with the repeat unit shown in above-mentioned Formulas I or Formula II with higher bactericidal properties.In addition, the antibacterial ultrafiltration membrane is separated by filtration performance with good；It can be stabilized in air and water；Recyclable regenerative；It is environment-friendly, non-corrosiveness.Test result indicates that：Antibacterial ultrafiltration membrane provided by the invention is 90~100% to the sterilizing rate of Escherichia coli or bacillus subtilis；It is 90~100% to the sterilizing rate of Escherichia coli or bacillus subtilis after placing 6 months in atmosphere；To the rejection of bovine serum albumin more than 99.2%.
Description
Technical field
The present invention relates to separation membrane technical field, more particularly to a kind of antibacterial ultrafiltration membrane and preparation method thereof and film are again
Generation method.
Background technology
Membrane separation technique is contemporary new separation technology, has efficient, easy to operate, free from environmental pollution, low energy consumption etc. prominent
Go out advantage, be widely used to the fields such as water resource, environment, food and biological medicine.Film (or is according to the difference in its aperture
Molecular cut off), microfiltration membranes, milipore filter, NF membrane and reverse osmosis membrane can be divided into.
Ultrafiltration is the membrane separation technique to emerge in the past 30 years, is widely used in macromolecular composition and low molecule quality material
Separation.Milipore filter in use, with the extension of usage time, the problem of all inevitably running into fouling membrane.It is super
The pollution of filter membrane can substantially be divided into：Organic matter and colloid pollute in absorption caused by film adsorption and by microorganism (as carefully
Bacterium) caused by microorganism pollution.Wherein, microorganism pollution is the limitation wide variety of principal element of milipore filter.Microorganism is super
After filter membrane surface absorption can amount reproduction, cause declining to a great extent for membrane flux and separating property, increase use cost.Therefore, it is anxious
The seperation film with antibiotic property need to be developed, prevents the biological pollution of milipore filter.
The document reported at present mainly using polysulfones, Kynoar as ultrafiltration membrane material, realized by adding antiseptic,
Common antiseptic includes metal and oxidized metal nanoparticle (such as nanometer Ag, TiO2, copper etc.), quaternary ammonium salt.Containing metal and
Oxidized metal bacteriostatic agent is easily lost in use, and anti-microbial property declines and easily environment is damaged.Contain quaternary ammonium salt
Antibacterial film long-time use after be also easy to produce drug resistance, reduce its anti-microbial property.
The content of the invention
In view of this, it is an object of the invention to provide a kind of antibacterial ultrafiltration membrane and preparation method thereof and film renovation process,
Antibacterial ultrafiltration membrane provided by the invention has excellent antibiotic property.
The invention provides a kind of antibacterial ultrafiltration membrane, as the ultrafiltration membrane material of the repeat unit shown in Formulas I or Formula II
It is prepared：
Preferably, the number-average molecular weight of the ultrafiltration membrane material is the g/mol of 100,000 g/mol~250,000.
Preferably, the thickness of the antibacterial ultrafiltration membrane is 50~500 μm.
The invention provides a kind of preparation method of antibacterial ultrafiltration membrane described in above-mentioned technical proposal, comprise the following steps：
Milipore filter is prepared using phase conversion method, preparing the material used in milipore filter includes PAEK or polyether sulphone,
The PAEK has the repeat unit shown in formula III：
The polyether sulphone has the repeat unit shown in formula IV：
Contacted by the milipore filter and containing solutions of chlorine, reacted, obtain antibacterial ultrafiltration membrane.
Preferably, it is described containing solution of the solutions of chlorine selected from liquor natrii hypochloritis and/or containing calcium hypochlorite.
Preferably, the mass fraction of the liquor natrii hypochloritis is 0.01~10%；In the solution containing calcium hypochlorite
The mass fraction of calcium hypochlorite is 0.1~30%.
Preferably, the solvent in the casting solution be selected from dimethylformamide, dimethyl acetamide, methyl pyrrolidone and
One or more in dimethyl sulfoxide (DMSO).
Preferably, the temperature of the reaction is 5 DEG C~35 DEG C；
The time of the reaction is 5min~24h.
The invention provides a kind of renovation process of antibacterial ultrafiltration membrane, comprise the following steps：
Anti-microbial property is declined into 70%~100% antibacterial ultrafiltration membrane and containing solutions of chlorine contact, reacted, obtaining can be again
Raw antibacterial ultrafiltration membrane；
The antibacterial ultrafiltration membrane is preparation method described in antibacterial ultrafiltration membrane described in above-mentioned technical proposal or above-mentioned technical proposal
The antibacterial ultrafiltration membrane of preparation.
A kind of ultrafiltration membrane material system the invention provides antibacterial ultrafiltration membrane as the repeat unit shown in Formulas I or Formula II
It is standby to form, N-Cl keys are included in the repeat unit shown in the Formulas I or Formula II, make the repetition for having shown in above-mentioned Formulas I or Formula II
Antibacterial ultrafiltration membrane prepared by the ultrafiltration membrane material of unit has higher bactericidal properties.In addition, the antibacterial ultrafiltration membrane has well
It is separated by filtration performance；It can be stabilized in air and water；Recyclable regenerative；It is environment-friendly, non-corrosiveness.Experimental result table
It is bright：Antibacterial ultrafiltration membrane provided by the invention is 90~100% to the sterilizing rate of Escherichia coli or bacillus subtilis；In atmosphere
It is 90~100% to the sterilizing rate of Escherichia coli or bacillus subtilis after placing 6 months；Retention to bovine serum albumin
Rate is more than 99.2%.
Brief description of the drawings
The antibiotic property test chart for the antibacterial ultrafiltration membrane that Fig. 1 is blank group 1, prepared by embodiment 1,3 and 5；
The antibiotic property test chart for the antibacterial ultrafiltration membrane that Fig. 2 is blank group 2, prepared by embodiment 2,4 and 6.
Embodiment
The invention provides a kind of antibacterial ultrafiltration membrane, as the ultrafiltration membrane material of the repeat unit shown in Formulas I or Formula II
It is prepared：
In the present invention, the number-average molecular weight of the ultrafiltration membrane material is preferably the g/mol of 100,000 g/mol~250,000.
In the present invention, the thickness of the antibacterial ultrafiltration membrane is preferably 50~500 μm.In the present invention, the antibacterial surpasses
The pure water flux of filter membrane is 60~1000L/m2h；Antibacterial ultrafiltration membrane is to the rejection of bovine serum albumin more than 99%.
The invention provides a kind of preparation method of antibacterial ultrafiltration membrane described in above-mentioned technical proposal, comprise the following steps：
Milipore filter is obtained using phase conversion method, preparing the material used in milipore filter includes PAEK or polyether sulphone,
The PAEK has the repeat unit shown in formula III：
The polyether sulphone has the repeat unit shown in formula IV：
Contacted by the milipore filter and containing solutions of chlorine, reacted, obtain antibacterial ultrafiltration membrane.
Preparation method process provided by the invention is simple, and reaction condition is gentle, and cost is low.
The present invention obtains milipore filter using phase conversion method, and preparing the material used in milipore filter includes PAEK or poly- virtue
Ether sulfone, the PAEK have the repeat unit shown in formula III：
The polyether sulphone has the repeat unit shown in formula IV：
In the present invention, the process that milipore filter is obtained using phase conversion method is preferably included：
Casting solution is cured successively and film forming, obtain milipore filter.
In the specific embodiment of the invention, the preparation process of the casting solution is preferably made by following methods：
PAEK with repeat unit shown in formula III or the polyether sulphone with repeat unit shown in formula IV are dissolved
In a solvent, deaeration and curing are then carried out successively, obtain casting solution.
In the present invention, the PAEK with repeat unit shown in formula III is preferably according to document Zhonggang
Wang, Tianlu Chen, and Jiping Xu, Hydrogen-Bonding in Cardo Copoly (aryl ether
Ketone) s and Its Effects on the Permeation Behavior, Macromolecules 2007,40,
It is prepared by 3238~3245 preparation methods recorded.In the present invention, the polyarylether with repeat unit shown in formula III
The number-average molecular weight of ketone is preferably the g/mol of 100,000 g/mol~250,000.
In the present invention, the polyether sulphone with repeat unit shown in formula IV is preferably according to document Qiang Zhang,
Suobo Zhang, Weihui Bi, Synthesis and properties of amphiphilic poly (ethylene
oxide)-grafted cardo poly(aryl ether sulfone)copolymers,Polymer52(2011),5471
It is prepared by~5478 preparation methods recorded.In the present invention, the number with the polyether sulphone of repeat unit shown in IV
Average molecular weight is preferably the g/mol of 100,000 g/mol~250,000.
In the present invention, the solvent is preferably selected from dimethylformamide, dimethyl acetamide, methyl pyrrolidone and two
One or more in methyl sulfoxide.
The present invention does not have special limitation to the method for the deaeration and curing, using well known to those skilled in the art de-
Bubble and the technical scheme of curing.The present invention cures 6~14 hours preferably in 28~32 DEG C of thermostatic chamber, more preferably 30
Cured 12 hours at DEG C.
In the present invention, the mass fraction of the casting solution is preferably 12~30%, and more preferably 15%~21%.
Casting solution is preferably carried out film forming by the present invention on a glass.Present invention preferably employs known to those skilled in the art
Scraper carry out film forming.In the present invention, the knife seam of the scraper is preferably 50~500 μm.
After the present invention completes knifing, preferably it is placed instantly into water and carries out inversion of phases, obtain milipore filter.In the present invention
In, the temperature of the inversion of phases is preferably 10 DEG C~50 DEG C.The present invention is preferably after inversion of phases terminates, by obtained milipore filter
Residual solvent be removed.Present invention preferably employs the removal that deionized water carries out residual solvent.In the specific reality of the present invention
Apply in example, the milipore filter immersion of preparation is removed residual solvent by the present invention in deionized water.
After obtaining milipore filter, the present invention contacts by the milipore filter and containing solutions of chlorine, is reacted, obtains antibacterial ultrafiltration
Film.
In the present invention, it is described to be preferably selected from liquor natrii hypochloritis and/or solution containing calcium hypochlorite containing solutions of chlorine；It is described
The mass fraction of liquor natrii hypochloritis is preferably 0.01~10%, and more preferably 1%~8%；In the specific embodiment of the present invention
In, the mass fraction of the liquor natrii hypochloritis is specially 1%, 5% or 10%.In the present invention, it is described containing calcium hypochlorite
The mass fraction of calcium hypochlorite is preferably 0.1~30% in solution, and more preferably 1~25%；In the specific embodiment of the present invention
In, the solution containing calcium hypochlorite is specially Eusol；The mass fraction of calcium hypochlorite is in the Eusol
10%.
In the present invention, the temperature of the reaction is preferably 5 DEG C~35 DEG C, more preferably 15 DEG C~25 DEG C；The reaction
Time be preferably 5min~24h, more preferably 1h~2h.
Preparation method process provided by the invention is simple, and reaction condition is gentle, and cost is low.
The invention provides a kind of renovation process of antibacterial ultrafiltration membrane, comprise the following steps：
Anti-microbial property is declined into 70%~100% antibacterial ultrafiltration membrane and containing solutions of chlorine contact, reacted, obtaining can be again
Raw antibacterial ultrafiltration membrane；
The antibacterial prepared using preparation method described in antibacterial ultrafiltration membrane described in above-mentioned technical proposal or above-mentioned technical proposal is surpassed
Filter membrane.
In the present invention, the antibacterial ultrafiltration membrane that anti-microbial property declines is on the basis of the antibacterial ultrafiltration membrane before use.At this
In invention, N-Cl key sections therein are reduced to N-H keys after antibacterial ultrafiltration membrane sterilization, and anti-microbial property weakens, it is carried out again
It is raw, the antibacterial ultrafiltration membrane regenerated.The present invention containing solutions of chlorine and the antibacterial after sterilization using surpassing described in above-mentioned technical proposal
Filter membrane contacts, and is reacted, is regenerated.The present invention does not have special limit to the bacterium of the use environment of the antibacterial ultrafiltration membrane
System.In the present invention, the bacterium is preferably Escherichia coli and/or bacillus subtilis.
In order to further illustrate the present invention, with reference to embodiment to a kind of antibacterial ultrafiltration membrane provided by the invention and its system
Preparation Method and film renovation process are described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1
1) preparation of antibacterial ultrafiltration membrane：
It is 18% that the PAEK that molecular weight is 200,000 g/mol, which is dissolved in dimethyl acetamide, and is made into mass fraction
PAEK solution, it is allowed to fully dissolve, filters off except being cured 12 hours in 30 DEG C of thermostatic chambers after insoluble matter deaeration, cast
Film liquid；With scraper, knifing, knife stitch 150 μm, glass plate are put into deionized water immediately carried out afterwards on clean glass plate
Inversion of phases, after inversion of phases is complete, immersion removal residual solvent, obtains milipore filter in deionized water；
The milipore filter of preparation is immersed in liquor natrii hypochloritis (mass concentration 1%) 5min.30 DEG C of washing residual hypochlorous acid
Sodium, and water is constantly changed, except a small amount of sodium hypochlorite remained in striping, to obtain antibacterial ultrafiltration membrane.
2) the anti-microbial property experiment of antibacterial ultrafiltration membrane
This experiment is using E. coli K12 (MG1655) as the bacteriostasis property for examining antibacterial ultrafiltration membrane.
Culture medium prescription used is as follows in experiment：
LB fluid nutrient mediums：1% tryptone, 0.5% yeast extract, 1% sodium chloride, pH value 7.0；
LB solid mediums：1% tryptone, 0.5% yeast extract, 1% sodium chloride, pH value 7.0,1.6% agar
Powder.
E.coli is inoculated in 5mL LB fluid nutrient mediums, is centrifuged after 37 DEG C of temperature, 200rpm concussions 12h, thalline is used
Phosphate buffer solution (PBS) washing centrifugation 3 times, is made into containing 106Individual/mL bacterium solutions.20 μ L are taken to be added to the above-mentioned anti-of 2cm × 2cm
On bacterium milipore filter, a piece of identical film is then covered in the top of film, top presses a sterile weight it is fully contacted 30min；
Then two panels film is dipped into fully shaking 20min in the hypo solution that 5mL mass fractions are 3%, 100 is taken after dilution
μ L are applied on LB solid mediums.Take 20 μ L bacterium solutions (106Individual/mL) it is added in 5mL hypo solutions, taken after dilution
It is 1,37 DEG C of culture 24h of blank group that 100 μ L, which are applied on LB solid mediums, and it is 90% to calculate sterilizing rate.Antibacterial test figure is shown in figure
1.The antibiotic property test chart for the antibacterial ultrafiltration membrane that Fig. 1 is blank group 1, prepared by embodiment 1,3 and 5.
Antibacterial ultrafiltration membrane is soaked in 10% liquor natrii hypochloritis after 4h and takes out washing, before and after immersion liquor natrii hypochloritis
Pure water flux is respectively 244L/m2h、239L/m2H, and the rejection of 1g/L bovine serum albumin is basically unchanged, it is maintained at
More than 99.8%.
Antibacterial ultrafiltration membrane is placed 6 months in the laboratory of normal lighting conditions, using E.coli K12 (MG1655)
The bacteriostasis property of film is examined, using above-mentioned antibacterial detection method, it is 90% to calculate sterilizing rate.
Embodiment 2
1) preparation of antibacterial ultrafiltration membrane：
It is 15% that the PAEK that molecular weight is 120,000 g/mol, which is dissolved in dimethyl acetamide, and is made into mass fraction
PAEK solution, it is allowed to fully dissolve, filters off except being cured 12 hours in 30 DEG C of thermostatic chambers after insoluble matter deaeration, cast
Film liquid；With scraper, knifing, knife stitch 200 μm, glass plate are put into deionized water immediately carried out afterwards on clean glass plate
Inversion of phases, after inversion of phases is complete, immersion removal residual solvent, obtains milipore filter in deionized water；
The milipore filter of preparation is immersed in liquor natrii hypochloritis (mass concentration 5%) 30min, 30 DEG C of washing residual time chlorine
Soaked one day in water after sour sodium, and constantly change water, except a small amount of sodium hypochlorite remained in striping, to obtain antibacterial and surpass
Filter membrane.
2) the anti-microbial property experiment of antibacterial ultrafiltration membrane
The biocidal property of film is examined in this experiment using bacillus subtilis Bacillus subtilis (CGMCC 1.1390)
Energy.
Bacillus subtilis are inoculated in 5mL LB fluid nutrient mediums, after 37 DEG C of temperature, 200rpm concussions 12h
Centrifugation, thalline wash centrifugation 3 times with phosphate buffer solution (PBS), are made into containing 106Individual/mL bacterium solutions.Take 20 μ L be added to 2cm ×
On 2cm above-mentioned antibacterial ultrafiltration membrane, a piece of identical film is then covered in the top of film, top presses a sterile weight to make its abundant
Contact 30min；Then two panels film is dipped into fully shaking 20min in the hypo solution that 5mL mass fractions are 3%,
Take 100 μ L to be applied on LB solid mediums after dilution, take 20 μ L bacterium solutions (106Individual/mL) it is added to 5mL hypo solutions
In, it is 2,37 DEG C of culture 24h of blank group to take 100 μ L to be applied on LB solid mediums after dilution, and it is 90% to calculate sterilizing rate, antibacterial
Test chart is shown in Fig. 2, the antibiotic property test chart for the antibacterial ultrafiltration membrane that Fig. 2 is blank group 2, prepared by embodiment 2,4 and 6.According to above-mentioned
Method detects to prepared antibacterial ultrafiltration membrane, sterilizing rate 95.2%.Antibacterial test figure is shown in Fig. 2.
Antibacterial ultrafiltration membrane is soaked in 10% liquor natrii hypochloritis after 4h and takes out washing, before and after immersion liquor natrii hypochloritis
Pure water flux is respectively 625L/m2h、630L/m2H, and the rejection of 1g/L bovine serum albumin is basically unchanged, it is maintained at
More than 99.5%.
Antibacterial ultrafiltration membrane is placed 6 months in the laboratory of normal lighting conditions, using bacillus subtilis
Bacillus subtilis (CGMCC 1.1390) examine the bacteriostasis property of antibacterial ultrafiltration membrane, and it is 94.9% to calculate sterilizing rate.
Embodiment 3
1) preparation of antibacterial ultrafiltration membrane：
It is 15% that the PAEK that molecular weight is 150,000 g/mol, which is dissolved in dimethyl acetamide, and is made into mass fraction
PAEK solution, it is allowed to fully dissolve, filters off except being cured 12 hours in 30 DEG C of thermostatic chambers after insoluble matter deaeration, cast
Film liquid；With scraper, knifing, knife stitch 100 μm on clean glass plate.Glass plate is put into deionized water immediately afterwards.Phase turns
After changing completely, immersion removal residual solvent, obtains milipore filter in deionized water；
The milipore filter of preparation is immersed in Eusol (concentration 10%) 30min.After 30 DEG C of washing residual sodium hypochlorite
Soaked one day in water, and constantly change water, except a small amount of sodium hypochlorite remained in striping, to obtain antibacterial ultrafiltration membrane.
2) the anti-microbial property experiment of antibacterial ultrafiltration membrane
This experiment is using E. coli K12 (MG1655) as the bacteriostasis property for examining antibacterial ultrafiltration membrane.By reality
The detection method for applying example 1 detects to prepared antibacterial ultrafiltration membrane film, sterilizing rate 94.2%.Antibacterial test figure is shown in Fig. 1.
Antibacterial ultrafiltration membrane is soaked in 10% liquor natrii hypochloritis after 4h and takes out washing, before and after immersion liquor natrii hypochloritis
Pure water flux is respectively 885L/m2h、876L/m2H, and the rejection of 1g/L bovine serum albumin is basically unchanged, it is maintained at
More than 99.2%.
Antibacterial ultrafiltration membrane is placed 6 months in the laboratory of normal lighting conditions, using E.coli K12 (MG1655)
The bacteriostasis property of film is examined, using above-mentioned antibacterial detection method, it is 93.8% to calculate sterilizing rate.
Embodiment 4
1) preparation of antibacterial ultrafiltration membrane：
It is 18% that the PAEK that molecular weight is 200,000 g/mol, which is dissolved in dimethyl acetamide, and is made into mass fraction
PAEK solution, it is allowed to fully dissolve, filters off except being cured 12 hours in 30 DEG C of thermostatic chambers after insoluble matter deaeration, cast
Film liquid, with scraper, knifing, knife stitch 200 μm, glass plate are put into deionized water immediately carried out afterwards on clean glass plate
Inversion of phases, after inversion of phases is complete, immersion removal residual solvent, obtains milipore filter in deionized water；
The milipore filter of preparation is immersed in Eusol (mass concentration 10%) 5h, 30 DEG C of washing residual sodium hypochlorite
Soaked one day in water afterwards, and constantly change water, except a small amount of sodium hypochlorite remained in striping, to obtain antibacterial ultrafiltration
Film.
2) the anti-microbial property experiment of antibacterial ultrafiltration membrane
This experiment is using bacillus subtilis Bacillus subtilis (CGMCC 1.1390) as inspection antibacterial ultrafiltration
The bacteriostasis property of film.
Prepared antibacterial ultrafiltration membrane film is detected by the detection method of embodiment 2, sterilizing rate 100%.Antibacterial
Test chart is shown in Fig. 2.
Antibacterial ultrafiltration membrane is soaked in 10% liquor natrii hypochloritis after 4h and takes out washing, before and after immersion liquor natrii hypochloritis
Pure water flux is respectively 123L/m2h、125L/m2H, and the rejection of 1g/L bovine serum albumin is basically unchanged, it is maintained at
More than 99.9%.
Antibacterial ultrafiltration membrane is placed 6 months in the laboratory of normal lighting conditions, using bacillus subtilis
Bacillus subtilis (CGMCC 1.1390) examine the bacteriostasis property of film, using above-mentioned antibacterial detection method, calculate sterilization
Rate is 100%.
Embodiment 5
1) preparation of antibacterial ultrafiltration membrane：
It is 18% that the polyether sulphone that molecular weight is 180,000 g/mol, which is dissolved in dimethyl acetamide, and is made into mass fraction
Polyether sulphone solution, it is allowed to fully dissolve, filters off except being cured 12 hours in 30 DEG C of thermostatic chambers after insoluble matter deaeration, cast
Film liquid, with scraper, knifing, knife stitch 100 μm, glass plate are put into deionized water immediately carried out afterwards on clean glass plate
Inversion of phases, after inversion of phases is complete, immersion removal residual solvent, obtains milipore filter in deionized water；
The milipore filter of preparation is immersed in liquor natrii hypochloritis (concentration 10%) 2h, after 30 DEG C of washing residual sodium hypochlorite
Soaked one day in water, and constantly change water, except a small amount of sodium hypochlorite remained in striping, to obtain antibacterial ultrafiltration membrane.
2) the anti-microbial property experiment of antibacterial ultrafiltration membrane
This experiment is using E. coli K12 (MG1655) as the bacteriostasis property for examining antibacterial ultrafiltration membrane.
Prepared antibacterial ultrafiltration membrane film is detected by the detection method of embodiment 1, sterilizing rate 100%.Antibacterial
Test chart is shown in Fig. 1.
Antibacterial ultrafiltration membrane is soaked in 10% liquor natrii hypochloritis after 4h and takes out washing, before and after immersion liquor natrii hypochloritis
Pure water flux is respectively 462L/m2h、460L/m2H, and the rejection of 1g/L bovine serum albumin is basically unchanged, it is maintained at
More than 99.8%.
Antibacterial ultrafiltration membrane is placed 6 months in the laboratory of normal lighting conditions, using E.coli K12 (MG1655)
The bacteriostasis property of film is examined, using above-mentioned antibacterial detection method, it is 100% to calculate sterilizing rate.
Embodiment 6
1) preparation of antibacterial ultrafiltration membrane：
It is 20% that the polyether sulphone that molecular weight is 200,000 g/mol, which is dissolved in dimethyl acetamide, and is made into mass fraction
Polyether sulphone solution, it is allowed to fully dissolve, filters off except being cured 12 hours in 30 DEG C of thermostatic chambers after insoluble matter deaeration, cast
Film liquid, with scraper, knifing, knife stitch 200 μm, glass plate are put into deionized water immediately carried out afterwards on clean glass plate
Inversion of phases, after inversion of phases is complete, immersion removal residual solvent, obtains milipore filter in deionized water；
The milipore filter of preparation is immersed in Eusol (mass concentration 10%) 2h, after 30 DEG C of washing residual bleaching powder
Soaked one day in water, and constantly change water, except a small amount of sodium hypochlorite remained in striping, to obtain antibacterial ultrafiltration membrane.
2) the anti-microbial property experiment of antibacterial ultrafiltration membrane
This experiment is using bacillus subtilis Bacillus subtilis (CGMCC 1.1390) as inspection antibacterial ultrafiltration
The bacteriostasis property of film.
Prepared antibacterial ultrafiltration membrane is detected by the detection method of embodiment 2, sterilizing rate 100%.Antibacterial is surveyed
Attempt to see Fig. 2.
Antibacterial ultrafiltration membrane is soaked in 10% liquor natrii hypochloritis after 4h and takes out washing, before and after immersion liquor natrii hypochloritis
Pure water flux is respectively 88L/m2h、87L/m2H, and the rejection of 1g/L bovine serum albumin is basically unchanged, it is maintained at
100%.
Antibacterial ultrafiltration membrane is placed 6 months in the laboratory of normal lighting conditions, using bacillus subtilis
Bacillus subtilis (CGMCC 1.1390) examine the bacteriostasis property of film, using above-mentioned antibacterial detection method, calculate sterilization
Rate is 100%.
Embodiment 7~12
Film after embodiment 1~6 is sterilized is to be immersed in sodium hypochlorite again after the treated film of sodium thiosulfate washs
2h in solution (mass concentration 5%), 30 DEG C of washings are soaked one day after remaining sodium hypochlorite in water, and constantly change water, to
Except a small amount of sodium hypochlorite remained in striping.The bacteriostasis property of film is examined using E. coli K12 (MG1655),
Prepared film is detected by the detection method of embodiment 1, sterilizing rate is 100%.
As seen from the above embodiment, the invention provides a kind of antibacterial ultrafiltration membrane, as the repetition shown in Formulas I or Formula II
The ultrafiltration membrane material of unit is prepared, and N-Cl keys are included in the repeat unit shown in the Formulas I or Formula II, make have above-mentioned formula
Antibacterial ultrafiltration membrane prepared by the ultrafiltration membrane material of I or the repeat unit shown in Formula II has higher bactericidal properties.In addition, the antibacterial
Milipore filter is separated by filtration performance with good；It can be stabilized in air and water；Recyclable regenerative；It is environment-friendly, nothing
Corrosivity.Test result indicates that：Antibacterial ultrafiltration membrane provided by the invention is to the sterilizing rate of Escherichia coli or bacillus subtilis
90~100%；It is 90~100% to the sterilizing rate of Escherichia coli or bacillus subtilis after placing 6 months in atmosphere；
To the rejection of bovine serum albumin more than 99.2%.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of antibacterial ultrafiltration membrane, it is prepared by the ultrafiltration membrane material with the repeat unit shown in Formulas I or Formula II：
The number-average molecular weight of the ultrafiltration membrane material is the g/mol of 100,000 g/mol~250,000；
The thickness of the antibacterial ultrafiltration membrane is 50~500 μm.
2. the preparation method of antibacterial ultrafiltration membrane, comprises the following steps described in a kind of claim 1：
Milipore filter is obtained using phase conversion method, preparing the material used in milipore filter includes PAEK or polyether sulphone, described
PAEK has the repeat unit shown in formula III：
The polyether sulphone has the repeat unit shown in formula IV：
The solvent prepared in the casting solution of milipore filter use is selected from dimethylformamide, dimethyl acetamide, methyl pyrrolidone
With the one or more in dimethyl sulfoxide (DMSO)；
Contacted by the milipore filter and containing solutions of chlorine, reacted, obtain antibacterial ultrafiltration membrane.
3. preparation method according to claim 2, it is characterised in that it is described containing solutions of chlorine be selected from liquor natrii hypochloritis and/
Or the solution containing calcium hypochlorite.
4. preparation method according to claim 3, it is characterised in that the mass fraction of the liquor natrii hypochloritis is 0.01
~10%；The mass fraction of calcium hypochlorite is 0.1~30% in the solution containing calcium hypochlorite.
5. preparation method according to claim 2, it is characterised in that the temperature of the reaction is 5 DEG C~35 DEG C；
The time of the reaction is 5min~24h.
6. a kind of renovation process of antibacterial ultrafiltration membrane, comprises the following steps：
Anti-microbial property is declined into 70%~100% antibacterial ultrafiltration membrane and containing solutions of chlorine contact, is reacted, obtained reproducible
Antibacterial ultrafiltration membrane；
The antibacterial ultrafiltration membrane is preparation method described in antibacterial ultrafiltration membrane described in claim 1 or claim 2~5 any one
The antibacterial ultrafiltration membrane of preparation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510783084.5A CN105289339B (en) | 2015-11-16 | 2015-11-16 | A kind of antibacterial ultrafiltration membrane and preparation method thereof and film renovation process |
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| CN201510783084.5A CN105289339B (en) | 2015-11-16 | 2015-11-16 | A kind of antibacterial ultrafiltration membrane and preparation method thereof and film renovation process |
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| CN105289339A CN105289339A (en) | 2016-02-03 |
| CN105289339B true CN105289339B (en) | 2017-11-14 |
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