CN108404684A - A kind of preparation method of the anti-pollution PVDF seperation film of super hydrophilic modification - Google Patents
A kind of preparation method of the anti-pollution PVDF seperation film of super hydrophilic modification Download PDFInfo
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- CN108404684A CN108404684A CN201810207011.5A CN201810207011A CN108404684A CN 108404684 A CN108404684 A CN 108404684A CN 201810207011 A CN201810207011 A CN 201810207011A CN 108404684 A CN108404684 A CN 108404684A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
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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
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention relates to a kind of preparation methods of the anti-pollution PVDF seperation film of super hydrophilic modification, PVDF Surface Creation double bonds are handled using alkaline solution, the crosslinked hyperbranched polyethyleneimine of chemical bond is passed through on pvdf membrane surface by the addition reaction of amino alkene and amino-epoxy ring-opening reaction；The hyperbranched polyethyleneimine of film surface carries out amino-epoxy ring-opening reaction with epoxy prapanol solution and the pvdf membrane with antifouling property is made.Modified pvdf membrane has a large amount of amino and hydroxyl isoreactivity group so that the hydrophily of film surface greatly improves.The present invention solves the stronger hydrophobicity of PVDF seperation films itself, prevents pollutant in application process from easily adsorbing, being deposited in film surface or fenestra, improves the contamination resistance of film, extend the service life of film.The present invention is modified using chemical method, mild condition, easy to operate, does not need expensive instrument, and easy to spread, products therefrom is secured, has good antifouling property, in water treatment field there is potential extensive use to be worth.
Description
Technical field
The present invention relates to a kind of preparation method of the anti-pollution PVDF seperation film of super hydrophilic modification, belong to water process science with
Technical field.
Background technology
Membrane separation technique is widely used in embrane method Sewage with the advantages such as its accurate separation, efficiently purifying, environmentally protective
Water treatment field.Kynoar（PVDF）It is a kind of membrane material of function admirable, it has intensity height, high temperature resistant, chemically-resistant
The features such as corrosion.But in pvdf membrane isolation technics application process, pvdf membrane surface energy is low, has extremely strong hydrophobicity to lead to it
Flux is low, easy to pollute, seriously limits its application in embrane method sewage treatment field.Therefore, PVDF seperation films are carried out hydrophilic
It is modified, promote the antifouling property of film, prolonging service lifetime of film has become the hot spot of field of membrane preparation.
Has the relevant report being largely modified about PVDF seperation film antipollutions at present.Wherein, anti-by being constructed in film surface
Anti-contamination function bed boundary, the surface graft modification method for realizing pvdf membrane contamination control, the abundant, modification efficiency with its method of modifying
High advantage by pvdf membrane preparation field researcher extensive concern.For example, patent of invention CN107096398A is with over cure
Sour potassium is catalyst, makes 2- acrylamide-2-methylpro panesulfonic acids（AMPS）With methyl methacrylate（MMA）Reaction generates two
Pvdf membrane is carried out dehydrofluorination processing by parent's property copolymer, then using above-mentioned amphipathic copolymer as grafted monomers, improves pvdf membrane
Hydrophily improves the antifouling property of film.Patent of invention CN104043351A uses ultraviolet radioactive Graft Method, is with ceric sulfate
Initiator, using maleic anhydride as grafted monomers, graft on PVDF ultrafiltration membrane surface, reach resistant to pollution purpose.Patent of invention
After CN103736407A pre-processes PVDF microfiltration membranes dehydrofluorinations, using dibenzoyl peroxide as initiator, bored with aphthenic acids
Or it is that accelerating agent obtains hydrophilic pollution-resistant membrane using maleic anhydride as grafted monomers that Cai's acid, which bores,.But the above method of modifying is mostly
The linear polymerics modifying agent such as double ion type polymer and polyethylene glycol type polymer is grafted on into pvdf membrane material surface, by line
Property molecular chain structure influence（Steric effect）, hydrophilic radical modify negligible amounts, cause modifying agent film surface coverage rate low, antipollution
Improved efficiency is limited；In addition, the above method of modifying is complicated, severe reaction conditions, it is difficult to meet the needs of of commercially producing.
Hyperbranched polyethyleneimine is highly branched as one kind, and branched end has the polymerization of a large amount of amino active groups
Object has higher antipollution efficiency under identical grafting concentration than its linear analogues.The present invention is sub- using hyperbranched polyethylene
Amine is carrier, and a large amount of amino active group is introduced into film surface, increases the hydrophily of film, then overspending by ring-opening reaction
Change polyethyleneimine amine end and introduce electronegative hydroxyl, further promotes that film surface is hydrophilic while to improve the electricity of film surface negative
Property, it realizes the super hydrophilic modification of film surface, forms the PVDF seperation films with antipollution effect.The present invention is easy to operate, is easy to
Control, the anti-pollution layer being prepared is securely efficient, can efficiently solve the fouling membrane during membrane separation technique use and ask
Topic, the application for membrane material in fields such as water process provide technical support.
Invention content
Present invention aim to address the very strong hydrophobicitys of existing pvdf membrane, provide a kind of antipollution that Superhydrophilic is modified
The preparation method of PVDF seperation films.
The preparation method of the PVDF seperation films of super hydrophilic modification proposed by the present invention, separation membrane surface after modified can
It significantly improves film surface hydrophily, reduces the adherency in film surface of protein, polysaccharide, deposition, there is significantly antipollution effect.
To achieve the above object, the preparation side of the anti-pollution PVDF seperation film of a kind of super hydrophilic modification proposed by the present invention
Method, the pollution-resistant membrane utilize the crosslinked hyperbranched polyethyleneimine of chemical bond, by ring opening cross-linked epoxy propyl alcohol, carry out table
Face is modified and is prepared, and is as follows：
（1）Diamine is added in the sodium carbonate buffer for being 11.0 to pH；The diamine solution mass concentration be 8.0 ~
24.0%；
（2）Using PVDF seperation films as basement membrane, basement membrane is dipped into step（1）In the solution of gained, in 200 ~ 300 rpm, 20 ~
30o10 ~ 12 h are reacted under the conditions of C, by amino-alkene addition reaction and amino-epoxy ring-opening reaction, its surface are made to form ammonia salt
Compound layer, the PVDF seperation films after being activated are for use after wash clean；
（3）By step（2）Obtained PVDF seperation films are soaked in the ethanol solution of epoxychloropropane, under nitrogen protection, are added
Enter catalyst, in 100 ~ 200 rpm, 55 ~ 65o5 ~ 7 h are reacted under C, then sodium hydroxide solution is added dropwise, and 100 ~ 200
Rpm, 40 ~ 50oThe reaction was continued under C, and 3 ~ 5 h form epoxy compounds by phase transfer catalysis process in PVDF separation membrane surfaces
Layer, it is for use with ethyl alcohol, deionized water wash clean；The epoxychloropropane concentration of polymer solution is 1.0% ~ 3.0%；The catalyst
Mass concentration is 0.01 ~ 0.03；The catalyst is chloro quaternary ammonium salt catalyst；The concentration of sodium hydroxide solution is
0.01~0.03%；
（4）By hyperbranched polyethyleneimine ethanol solution and step（3）Middle gained PVDF seperation films are 70 ~ 90oUnder C reaction 24 ~
36h makes hyperbranched polyethyleneimine pass through chemical bond and is linked to step（3）Gained PVDF separation membrane surfaces, with ethyl alcohol, deionization
Washing is clean for use；Hyperbranched polyethyleneimine mass fraction is 2.5% ~ 7.5%；
（5）By step（4）It obtains PVDF seperation films to be immersed in methanol solution, epoxy prapanol is added dropwise, 200 ~ 300
Rpm, 20 ~ 30o10 ~ 12 h are reacted under the conditions of C makes the hyperbranched polyethyleneimine on its surface by amino-epoxy ring-opening reaction
Layer terminal amino group is covered by hydroxyl, forms super hydrophilic anti-pollution PVDF separation membrane material；The mass fraction of epoxy prapanol is
0.1%~5%；
（6）After reaction, super hydrophilic anti-pollution PVDF separation membrane material is taken out, is rinsed well simultaneously with ethyl alcohol, deionized water
Drying, obtains the PVDF seperation films with antifouling property.
In the present invention, step（1）The diamine is one or more of propane diamine, butanediamine or pentanediamine.
In the present invention, step（3）The chloro quaternary ammonium salt catalyst is benzyltriethylammoinium chloride, cetyl three
It is any in ammonio methacrylate or tetrabutylammonium chloride.
In the present invention, step（3）The polymer separation film immersion way is to be totally immersed into solution, and to be modified
It is face-up.
In the present invention, step（4）The weight average molecular weight of the hyperbranched polyethyleneimine is 600 g/mol, 10,000 g/
It is any in mol or 60,000 g/mol.
The beneficial effects of the present invention are：Compared with prior art, the membrane preparation method in the present invention innovatively uses table
Face, which is modified, will have the dissaving polymer of amino active group to be fixed on film surface, and pass through ring opening chemical bond cross-linked epoxy
Propyl alcohol is successfully made super hydrophilic modification, improves film to make film surface contain the hydrophilic radicals such as great amount of hydroxy group, amino
Antifouling property.Anti-bacterial and anti-fouling prepared by this method contaminates polymer-modified seperation film and has the following advantages：
(1) a kind of method in the hyperbranched hydrophilic modifying of surface of separating film of polymer is proposed, this method is with hyperbranched polyethylene
Imines is carrier layer, the antifouling property of film surface is improved by chemical bond cross-linked epoxy propyl alcohol, it is lasting, anti-that hydrophilicity is stablized
Pollutant performance dramatically increases；
(2) the PVDF separation membrane surfaces through hydrophilic modifying have great amount of hydroxy group group, compare traditional wire to the binding ability of hydrone
Property polyethyleneglycol derivative it is more strong, to the pollutants such as protein, polysaccharide have apparent anti-adhesion effect, antifouling property
Persistently；
(3) hyperbranched polyethyleneimine used in is cheap and easy to get, and surface has a large amount of active amine groups, is to carry out a variety of modifications
Good carrier；
(4) film forming condition is mild, and operation is easy, and equipment is cheap, and controllability is good, is easy industrializing implementation.
Description of the drawings
Fig. 1 is film P0, P-NH obtained by embodiment 12, P-EPI, P-HPEI and P-HPEI-GLY the water of different moments connect
Feeler variation diagram.
Fig. 2 is the clear water flux figure of film P0 and P-HPEI-GLY obtained by embodiment 1.
CLSM after Fig. 3 is protein, polysaccharide contacts 3 h with film P0 and P-HPEI-GLY obtained by embodiment 1 schemes, dyeing
Part is protein/polysaccharide.Figure（A）It is that CLSM schemes after protein contacts 3 h with 1 gained film P0 of embodiment, figure（B）It is protein
CLSM schemes after contacting 3 h with 1 gained film P-HPEI-GLY of embodiment, figure（C）It is after polysaccharide contacts 3 h with 1 gained film P of embodiment
CLSM schemes, figure（D）It is that CLSM schemes after polysaccharide contacts 3 h with 1 gained film P-HPEI-GLY of embodiment.
Fig. 4 is film P0 and P-HPEI-GLY dynamic anti-protein obtained by embodiment 1, polysaccharide pollutant performance statistics.Figure（A）
It is FRR, IFR, RFR after 1 gained film P0 and P-HPEI-GLY dead-end filtration of embodiment, 190 min using protein as pollutant
It is worth comparison diagram, figure（B）It is using polysaccharide as pollutant, after 1 gained film P0 and P-HPEI-GLY dead-end filtration of embodiment, 190 min
FRR, IFR, RFR value comparison diagram.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with attached drawing and specific implementation
Mode, the present invention will be described in further detail.It should be appreciated that the specific embodiments described herein are only explaining this
Invention, is not intended to limit the present invention.
Embodiment 1：
PVDF seperation films are impregnated into 24 h in clear water, remove the impurity of PVDF separation membrane surfaces（It is denoted as P0）.It will be preprocessed
Isolate film be placed at polytetrafluoroethylene (PTFE) closing box in（Single side reaction box）, configuration 1 M Putriscine be dissolved into carbonic acid
Sodium buffer solution（Adjust pH=11.0）In, 200 rpm, 25o12 h are reacted under the conditions of C, until having faint yellow ammonia salt chemical combination on film
Nitride layer occurs.Water, ethyl alcohol alternately 24 h of cleaning are used afterwards, 40oIt is dried in vacuo, obtains modified through the first step under the conditions of C
PVDF seperation films（It is denoted as P-NH2）.The film P-NH that will be obtained2It is face-up soaked in 150 mL absolute ethyl alcohols, is added dropwise thereto
3 mL epoxychloropropane carry out nitrogen filled protection to device, are slowly added to 40 mg benzyltriethylammoinium chlorides, in 100 rpm,
65o5 h are reacted under C, then the 0.06 M sodium hydroxide solutions of 5 mL are added dropwise, and in 100 rpm, 40oThe reaction was continued under C 3
h.Water, ethyl alcohol alternately 24 h of cleaning are used afterwards, 40oIt is dried in vacuo under the conditions of C, obtains the crosslinked PVDF separation of epoxy compounds
Film（It is denoted as P-EPI）.Obtained film P-EPI is soaked in the hyperbranched polyethyleneimine of 30 g/L（Weight average molecular weight is 10,
000 g/mol）Ethanol solution in, in 100 rpm, 85o24 h are reacted under C, and hyperbranched polyethyleneimine is made to pass through chemical bond
It is linked to PVDF separation membrane surfaces.Water, ethyl alcohol alternately 24 h of cleaning are used afterwards, 40oIt is dried in vacuo, obtains hyperbranched under the conditions of C
The crosslinked PVDF seperation films of polyethyleneimine（It is denoted as P-HPEI）.By the crosslinked PVDF seperation films single side of hyperbranched polyethyleneimine
It is immersed in methanol solution, 0.5 mL epoxy prapanols is added dropwise, in 250 rpm, 25o10 h are reacted under the conditions of C, by epoxy third
Alcohol is fixed on hyperbranched polyethyleneimine surface by chemical bond.Water, ethyl alcohol alternately 24 h of cleaning are used afterwards, 40oIt is true under the conditions of C
Sky is dry, obtains super hydrophilic anti-pollution PVDF seperation film（It is denoted as P-HPEI-GLY）.
Embodiment 2：
PVDF seperation films are impregnated into 24 h in clear water, remove the impurity of PVDF separation membrane surfaces（It is denoted as P0）.It will be preprocessed
Isolate film be placed at polytetrafluoroethylene (PTFE) closing box in（Single side reaction box）, configuration 1 M Isosorbide-5-Nitrae-pentanediamine be dissolved into carbonic acid
Sodium buffer solution（Adjust pH=11.0）In, it is placed in shaking table, 200 rpm, 25o12 h are reacted under the conditions of C, until having on film yellowish
Color ammonia salt compound layer occurs.Water, ethyl alcohol alternately 24 h of cleaning are used afterwards, 40oIt is dried in vacuo, is obtained through the first step under the conditions of C
Modified PVDF seperation films（It is denoted as P-NH2）.The film P-NH that will be obtained2Face-up it is soaked in 150 mL absolute ethyl alcohols, to
3 mL epoxychloropropane are wherein added dropwise, nitrogen filled protection is carried out to device, 40 mg benzyltriethylammoinium chlorides are slowly added to, 100
Rpm, 65o5 h are reacted under C, then the 0.06 M sodium hydroxide solutions of 5 mL are added dropwise, and in 100 rpm, 40oContinue under C anti-
Answer 3 h.Water, ethyl alcohol alternately 24 h of cleaning are used afterwards, 40oIt is dried in vacuo under the conditions of C, obtains the crosslinked PVDF of epoxy compounds
Seperation film（It is denoted as P-EPI）.Obtained film P-EPI is soaked in the hyperbranched polyethyleneimine of 30 g/L（Weight average molecular weight is
60,000 g/mol）Ethanol solution in, in 100 rpm, 85o24 h are reacted under C, and hyperbranched polyethyleneimine is made to pass through chemistry
Key is linked to PVDF separation membrane surfaces.Water, ethyl alcohol alternately 24 h of cleaning are used afterwards, 40oIt is dried in vacuo, is overspend under the conditions of C
Change the crosslinked PVDF seperation films of polyethyleneimine（It is denoted as P-HPEI）.By the crosslinked PVDF seperation films list of hyperbranched polyethyleneimine
Face is immersed in methanol solution, and 0.5 mL epoxy prapanols are added dropwise, in 250 rpm, 25o10 h are reacted under the conditions of C, by epoxy
Propyl alcohol is fixed on hyperbranched polyethyleneimine surface by chemical bond.Water, ethyl alcohol alternately 24 h of cleaning are used afterwards, 40oUnder the conditions of C
Vacuum drying, obtains super hydrophilic anti-pollution PVDF seperation film（It is denoted as P-HPEI-GLY）.
Embodiment 3：
Contact angle is tested：Contact angle using contact angle tester test water on pvdf membrane surface.
After tested, the film P0 contact angles of 1 gained of embodiment are 85-95o, modified caudacoria P-HPEI and P-HPEI-GLY connects
Feeler is remarkably decreased than film P0 to 30-40 o, and it is down to 0 in 15 so, it was demonstrated that modified caudacoria hydrophily is good.
Embodiment 4：
Clear water flux is tested：Dead end mistakes under the conditions of 20 kPa of the film P0 and P-HPEI-GLY obtained by embodiment 1 are chosen respectively
Filter is intake as deionized water, and clear water flux both is recorded and calculate.
After tested, the film P0 clear water fluxes of 1 gained of embodiment are significantly less than Modified Membrane P-HPEI-GLY, it was demonstrated that Modified Membrane parent
It is aqueous good, it is consistent with contact angle test.
Embodiment 5：
Static anti-protein/polysaccharide absorption test：The anti-protein of film/polysaccharide experiment uses bovine serum albumin in the present invention
PBS solution and sodium alginate aqueous solution, a concentration of 50 mg/L.The PVDF original film P0 and antipollution in embodiment 1 are chosen respectively
Pvdf membrane P-HPEI-GLY cuts into 1 × 1 cm2Size is simultaneously immersed in protein solution/polysaccharide solution of 5 mL, 37oC
Under the conditions of shake 3 h in the dark, diaphragm is taken out and PBS solution/deionized water solution is used to rinse 2 times.Diaphragm is placed in load glass
Fluorescein isothiocynate is used in combination on piece（FITC）/ concanavalin A（Con A）Diaphragm is dyed, and 37oDark under the conditions of C
0.5 h of place's culture.Diaphragm PBS solution/the deionized water solution for having contaminated color is rinsed 2 times, mounting laser confocal scanning
Microscope（CLSM）It is observed.
It can be seen that the content of protein and polysaccharide pollutant on anti-pollution PVDF film P-HPEI-GLY by CLSM analyses
Considerably less than former film P0, illustrate that film P-HPEI-GLY has apparent anti-adhesion effect.
Embodiment 6：
Dynamic anti-protein/polysaccharide test：The film P0 and P-HPEI-GLY obtained by embodiment 1 is chosen respectively in 20 kPa conditions
Lower dead-end filtration, water inlet program are that -60 min protein of 20 min pure water/- 30 min pure water of polysaccharide solution is backwashed, altogether
Carry out 2 cycles.Record the attenuation of the flux of the two at any time.Restore ratio with water flux（FRR）, under irreversible water flux
Drop ratio（IFR）With opposite damage ratio（RFR）To weigh the antifouling property of film.The calculation formula of three is as follows：
Wherein,J rIndicate the flux restored after film is backwashed,J 0Indicate film initial flux,J pAfter indicating 60 min of fouling membrane
Stable water flux.
After tested, after protein or polysaccharide pollution, water flux restores ratio and is all remarkably higher than original film P-HPEI-GLY
Film P0, irreversible water flux ratio and opposite damage ratio are substantially less than former film P0, illustrate that Modified Membrane is not easy to be contaminated, are readily cleaned,
Antifouling property is good.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (5)
1. a kind of preparation method of the anti-pollution PVDF seperation film of super hydrophilic modification, it is characterised in that be as follows：
（1）Diamine is added in the sodium carbonate buffer for being 11.0 to pH；The diamine solution mass concentration be 8.0 ~
24.0%；
（2）Using PVDF seperation films as basement membrane, basement membrane is dipped into step（1）In acquired solution, in 200 ~ 300rpm, 20 ~ 30oC items
10 ~ 12 h are reacted under part, by amino-alkene addition reaction and amino-epoxy ring-opening reaction, its surface are made to form ammonia salt compound
Layer, the PVDF seperation films after activate, after wash clean for use；
（3）By step（2）It obtains PVDF seperation films to be soaked in the ethanol solution of epoxychloropropane, under nitrogen protection, be added
Catalyst, in 100 ~ 200rpm, 55 ~ 65o5 ~ 7 h are reacted under C, then sodium hydroxide solution is added dropwise, and 100 ~ 200
Rpm, 40 ~ 50oThe reaction was continued under C, and 3 ~ 5 h form epoxy compounds by phase transfer catalysis process in PVDF separation membrane surfaces
Layer, it is for use with ethyl alcohol, deionized water wash clean；The epoxychloropropane concentration of polymer solution is 1.0% ~ 3.0%；The catalyst
Mass concentration is 0.01 ~ 0.03, and the catalyst is chloro quaternary ammonium salt catalyst；The concentration of sodium hydroxide solution is
0.01~0.03%；
（4）By hyperbranched polyethyleneimine ethanol solution and step（3）Gained PVDF seperation films are 70 ~ 90o24 ~ 36h is reacted under C,
So that hyperbranched polyethyleneimine is passed through chemical bond and is linked to step（3）Gained PVDF separation membrane surfaces are washed with ethyl alcohol, deionization
It is clean for use；Hyperbranched polyethyleneimine mass fraction is 2.5% ~ 7.5%；
（5）By step（4）It obtains PVDF seperation films to be immersed in methanol solution, epoxy prapanol is added dropwise, 200 ~ 300
Rpm, 20 ~ 30o10 ~ 12 h are reacted under the conditions of C makes the hyperbranched polyethyleneimine on its surface by amino-epoxy ring-opening reaction
Layer terminal amino group is covered by hydroxyl, forms super hydrophilic anti-pollution PVDF separation membrane material；The mass fraction of epoxy prapanol is
0.1%~5%；
（6）After reaction, super hydrophilic anti-pollution PVDF separation membrane material is taken out, is rinsed well simultaneously with ethyl alcohol, deionized water
Drying, obtains the PVDF seperation films with antifouling property.
2. the preparation method of anti-pollution PVDF seperation film according to claim 1, which is characterized in that step（1）Described two
First amine is the one or more of propane diamine, butanediamine or pentanediamine.
3. the preparation method of anti-pollution PVDF seperation film according to claim 1, which is characterized in that step（3）Described
Chloro quaternary ammonium salt catalyst is any in benzyltriethylammoinium chloride, hexadecyltrimethylammonium chloride or tetrabutylammonium chloride
Kind.
4. the preparation method of antibacterial stable against biological contamination polymer separation film according to claim 1, which is characterized in that step
（3）The polymer separation film immersion way is to be totally immersed into solution, and to be modified face-up.
5. the preparation method of anti-pollution PVDF seperation film according to claim 1, which is characterized in that step（4）It is described super
The weight average molecular weight of branched polyethylene imine is any in 600 g/mol, 10,000 g/mol or 60,000 g/mol.
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