CN113083030A - Anti-pollution high-flux modified polymer separation membrane and preparation method thereof - Google Patents
Anti-pollution high-flux modified polymer separation membrane and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 41
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- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims abstract description 35
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
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- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to an anti-pollution high-flux modified polymer separation membrane and a preparation method thereof, wherein an acrylic acid monomer is added into an ammonium ferrous sulfate aqueous solution to prepare a grafted solution; and (3) putting the polymer separation membrane into the grafting solution, introducing inert gas to remove oxygen, and performing electron beam radiation grafting to obtain the modified polymer separation membrane. According to the invention, the acrylic monomer is grafted on the polymer separation membrane by radiation, so that the hydrophilicity of the membrane is obviously improved, and the water content is 3-5 times higher than that before modification; the water flux of the modified polymer separation membrane during filtering BSA solution is improved by 20-50% compared with the water flux during filtering pure water, the flux reduction rate is obviously reduced, and the membrane anti-pollution performance is obviously improved. The preparation method provided by the invention is simple to operate, low in cost, easy to realize industrial application and has important significance for promoting the application of the separation membrane.
Description
Technical Field
The invention relates to the technical field of surface modification of polymer separation membranes, in particular to an anti-pollution high-flux modified polymer separation membrane and a preparation method thereof.
Background
Membrane separation technologies that have gained in the 60's of the 20 th century have many advantages such as high efficiency, high selectivity, small footprint, low cost and low energy consumption. Due to its superior filtration and separation performance, it has played a great role in the field of water treatment.
However, membrane fouling is a bottleneck problem that limits the widespread use of membrane-process wastewater treatment technologies. The membrane pollution can cause the serious reduction of the membrane filtration performance, the filtration efficiency is influenced, and the membrane pollution can be removed to a certain extent by backwashing and chemical cleaning, but the operation cost and the threat to the secondary pollution of the environment are undoubtedly increased. There are many factors that cause membrane fouling, of which hydrophobic-hydrophobic interaction is considered to be the primary and major factor causing membrane fouling. Hydrophobic organic pollutants are easy to adsorb on the surface of a hydrophobic polymer membrane, so that the hydrophobic organic pollutants stay on the surface of the membrane to cause membrane pollution, and even part of the hydrophobic organic pollutants enter membrane pores to cause unrecoverable permanent pollution to the membrane. Researchers believe that developing hydrophilic, highly contaminant-resistant membranes can overcome this hydrophobic-to-hydrophobic force, thereby reducing membrane replacement and cleaning frequency, and thus cost.
Organic molecules having hydrophilic functional groups such as carboxyl groups and hydroxyl groups are widely used as hydrophilic substances, and are considered to have a great potential in improving the hydrophilicity of membranes. Numerous researchers have explored grafting hydrophilic organic molecules onto the surface of polymer membranes to improve the anti-fouling properties of the membranes. U.S. Pat. No. 4, 8550256, 1 reports the modification of methacrylate on polysulfone-based membranes by photo-grafting, and the results show that the grafted membranes have significantly improved resistance to contamination and possess anti-biofouling properties. One of the most commonly used methods for polymerization reaction is Atom Transfer Radical Polymerization (ATRP), Yen-Che Chiang et al graft sulfonated methyl acrylate on the surface of PVDF membrane by Atom Transfer Radical Polymerization (ATRP), the hydrophilicity of the grafted membrane surface is obviously increased, and the BSA solution of 1g/L is filtered circularly, so that only 13% of irreversible pollution is generated in the first circulation, and almost no further pollution is generated in the second circulation, and the anti-pollution capability of the membrane is improved. In chinese patent document CN1986038A, acrylic acid and sodium styrene sulfonate are grafted as grafting monomers to perform hydrophilization grafting on the surface of the fluoropolymer separation membrane, so that the contact angle of the PVDF membrane is reduced from 93 ° to 53 °, the contact angle of the Polytetrafluoroethylene (PTFE) membrane is reduced from 122 ° to 79 °, and the hydrophilicity is significantly improved. In addition, many organic monomers similar to acrylic acid are also used to improve the hydrophilicity of the membrane, for example, Masahide Taniguchi, etc. hydrophilic monomers are used to hydrophilically modify a Polyethersulfone (PES) membrane, and 6 hydrophilic monomers are selected in experiments, namely n-vinyl pyrrolidone, hydroxyethyl methacrylate, acrylic acid, acetamide glycolic acid, sulfopropyl methacrylic acid and 2-acrylamide-2-methyl-1-propanesulfonic acid. The anti-pollution performance of the grafted membrane is improved to different degrees, wherein the acrylic acid grafted membrane shows the strongest anti-pollution performance, and the irreversible pollution in the acrylic acid grafted membrane is 0. The chemical grafting method has positive experiment results on hydrophilicity and pollution resistance by modifying the surface of the grafted polymer membrane, but has various defects, such as harsh conditions of grafting reaction, difficult effective control of reaction, unsatisfactory grafting efficiency, large amount of catalyst and initiator, and the like. This undoubtedly raises the cost of the separation membrane application, and such complicated experimental conditions are an insurmountable challenge for large-scale industrial application. In addition, although the contamination resistance of the sewage solution after grafting is improved and the decrease of the membrane flux is slowed down when the sewage solution is filtered, the limitation that the water flux when the sewage solution is filtered is significantly lower than that when pure water is filtered is not broken. Therefore, the development of a more efficient, controllable and environment-friendly polymer separation membrane modification method is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an anti-pollution and high-flux modified polymer separation membrane and a preparation method thereof.
To this end, in a first aspect, the present invention provides a method for preparing an anti-fouling, high-flux modified polymer separation membrane, comprising the steps of:
adding acrylic acid monomers into the ammonium ferrous sulfate aqueous solution to prepare a grafting solution; and (3) putting the polymer separation membrane into the grafting solution, introducing inert gas to remove oxygen, and performing electron beam radiation grafting to obtain the modified polymer separation membrane.
Further, the acrylic monomer is selected from one or a combination of two of the following groups: acrylic acid, acrylamide.
Further, in the grafting solution, the mass fraction of the acrylic monomer is 0.5% to 10%, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.
The mass fraction of the acrylic monomer has obvious influence on the performance of the modified polymer separation membrane, and if the mass fraction is lower than 0.5%, the filtration advantage of pollutants (taking BSA as an example) is not obvious; if it is higher than 10%, the membrane pores are clogged seriously and the loss of water flux is excessive.
Further, in the ferrous ammonium sulfate aqueous solution, the mass fraction of ferrous ammonium sulfate is 0.1-0.3%.
According to the technical scheme of the invention, ammonium ferrous sulfate is used as a polymerization inhibitor in the grafting solution, and the function of the ammonium ferrous sulfate is mainly to prevent the acrylic monomer from generating homopolymerization reaction in the grafting solution.
In a specific embodiment, the ferrous ammonium sulfate solution is prepared according to the following steps: adding ammonium ferrous sulfate into deionized water, and ultrasonically stirring until the ammonium ferrous sulfate is completely dissolved.
Further, when adding acrylic monomers into the ferrous ammonium sulfate aqueous solution, the tail part of the dropping pipe containing the acrylic monomers is extended below the liquid level of the ferrous ammonium sulfate aqueous solution for dropping.
According to the technical scheme of the invention, the tail of the dripping pipe extends below the liquid level of the ammonium ferrous sulfate aqueous solution for dripping, so that the acrylic monomer can be prevented from reacting in the air.
Further, the polymer separation membrane is also pretreated by the following steps before being put into the grafting solution: and sequentially leaching and soaking the polymer separation membrane by using deionized water.
In a specific embodiment, the soaking time is 18-48h, preferably 20-26 h.
According to the technical scheme of the invention, residues brought into the polymer separation membrane in the production process can be removed by rinsing and soaking the polymer separation membrane.
Further, the pore size of the polymer separation membrane is 0.01-1 μm.
Furthermore, the radiation dose rate of the electron beam radiation grafting is 1.0-5.0kGy/h, and the radiation time is 5-15h, preferably 8-12 h.
Further, the electron beam radiation is grafted to Co 60Radiation grafting or Cs137And (4) radiation grafting.
Further, the inert gas is nitrogen or argon; the time for introducing the inert gas is 20-30 min.
Further, the polymer separation membrane is a polyvinylidene fluoride membrane, a polysulfone membrane, a polyethylene membrane, a polypropylene membrane, a polytetrafluoroethylene membrane, a polyether sulfone membrane, a polyamide membrane, or the like.
In one embodiment, the preparation method of the present invention comprises the following steps: putting the polymer separation membrane into a radiant tube, and adding the grafting solution into the radiant tube to ensure that the polymer separation membrane is completely immersed under the liquid level of the grafting solution; then filling inert gas to completely remove oxygen in the radiant tube, and sealing the radiant tube; and then placing the radiant tube in a radiation field to perform electron beam radiation.
In one embodiment, the preparation method of the present invention comprises the following steps:
(1) adding ferrous ammonium sulfate into deionized water to prepare a ferrous ammonium sulfate aqueous solution with the mass fraction of 0.1-0.3%;
(2) adding an acrylic monomer into the ferrous ammonium sulfate aqueous solution obtained in the step (1) to prepare a grafting solution with the mass fraction of the acrylic monomer of 0.5-10%;
(3) transferring a proper amount of the grafting solution prepared in the step (2) into a radiant tube, soaking the polymer separation membrane in the radiant tube, filling inert gas to remove oxygen, and sealing the radiant tube;
(4) and (4) placing the radiant tube processed in the step (3) in a radiation field, setting the radiation dose rate to be 1.0-5.0kGy/h and the radiation time to be 5-15h, and thus obtaining the anti-pollution high-flux modified polymer separation membrane.
In a second aspect of the invention, an anti-pollution high-flux modified polymer separation membrane is provided, which is prepared by the preparation method provided by the invention.
The present invention is based on previous studies (patent document CN201710183493.0), and studies the effect of various grafts on the performance and separation characteristics of a polymer membrane, and unexpectedly found that when grafting is performed with one or a combination of acrylic acid and acrylamide, the anti-pollution performance of the membrane is unexpectedly and significantly improved, specifically that: flux was anomalous when filtering BSA solution, with water flux 20% -50% higher when filtering BSA solution than when filtering pure water.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) according to the invention, the acrylic monomer is grafted on the polymer separation membrane by radiation, so that the anti-pollution capacity of the membrane is effectively improved, and the limitation that the water flux is lower than that of pure water during filtering BSA solution is broken through. Because the hydrophilicity of the grafted membrane is increased, the water content is obviously improved, the water content is 3-5 times higher than that before modification, and the direct attraction force with BSA is obviously weakened, so that the grafted membrane is very suitable for filtering BSA solution, and the following unexpected technical effects are achieved: when purified water and a BSA solution were filtered by circulation, the modified polymer separation membrane was found to have an abnormal flux when filtering the BSA solution, and the flux when filtering the BSA solution was 20% to 50% higher than the flux when filtering purified water.
(2) The invention realizes the hydrophilic modification of the polymer separation membrane by radiation grafting of acrylic monomers on the polymer separation membrane. The method has strong controllability, can realize accurate control of the grafting reaction only by adjusting the radiation metering, has simple equipment and low cost, and is easy to realize large-scale industrial application.
(3) According to the invention, the propylene monomer is grafted on the polymer separation membrane by radiation, only a small amount of polymerization inhibitor is used in the process, and the secondary pollution to the environment is extremely low.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. In the drawings:
FIG. 1 is a schematic diagram of an experimental process of a preparation method provided by the present invention;
FIG. 2 is a drawing of an Atomic Force Microscope (AFM) of the surface of a film before and after radiation grafting according to a preparation method provided by the present invention; wherein a and c are before radiation grafting, and b and d are after radiation grafting.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Example 1
Firstly, deionized water is used for preparing 500mL of 0.1% ammonium ferrous sulfate aqueous solution, and the ammonium ferrous sulfate has the function of preventing a monomer from generating homopolymerization in the solution. Then, 2.5g of acrylic acid (in order to prevent the acrylic acid from reacting in the air, the tail of the dropping tube should be extended below the liquid level of the ammonium ferrous sulfate aqueous solution during dropping) was dropped into the prepared ammonium ferrous sulfate aqueous solution to prepare a graft solution.
In the preparation stage of the PVDF membrane, PVDF with a pore diameter of 0.1 mu m and non-woven fabric support is cut into a membrane with the size of 10cm multiplied by 10cm, is washed by deionized water and is soaked in the deionized water for 24 hours. The clean PVDF membrane was then placed in an irradiation tube, and 200mL of the grafting solution was added to the irradiation tube. The radiant tube was sealed with vaseline and purged with nitrogen for 30min to completely remove the air from the radiant tube. Finally, the radiation tube soaked with PVDF is placed in a radiation field, the radiation dose rate is set to be 1kGy/h, the radiation time is set to be 10h, and finally, the grafted PVDF membrane is prepared and is marked as membrane A.
Example 2
Firstly, deionized water is used for preparing 500mL of 0.1% ammonium ferrous sulfate aqueous solution, and the ammonium ferrous sulfate has the function of preventing a monomer from generating homopolymerization in the solution. Then, 3g of acrylamide was added dropwise to the prepared ammonium ferrous sulfate aqueous solution (in order to prevent the acrylamide from reacting in the air, the end of the dropping tube should be extended below the liquid level of the ammonium ferrous sulfate aqueous solution during the addition), to prepare a graft solution.
In the preparation stage of the PVDF membrane, PVDF with a pore diameter of 0.1 mu m and non-woven fabric support is cut into a membrane with the size of 10cm multiplied by 10cm, is washed by deionized water and is soaked in the deionized water for 24 hours. The clean PVDF membrane was then placed in an irradiation tube, and 200mL of the grafting solution was added to the irradiation tube. The radiant tube was sealed with vaseline and purged with nitrogen for 30min to completely remove the air from the radiant tube. Finally, the radiation tube soaked with PVDF is placed in a radiation field, the radiation dose rate is set to be 5kGy/h, the radiation time is set to be 10h, and finally, the grafted PVDF membrane is obtained and is marked as a membrane B.
Example 3
Firstly, deionized water is used for preparing 500mL of 0.3 percent ammonium ferrous sulfate aqueous solution, and the ammonium ferrous sulfate has the function of preventing the monomer from generating homopolymerization in the solution. Then, 1g of acrylic acid and 2g of acrylamide are added dropwise to the prepared ammonium ferrous sulfate aqueous solution (in order to prevent the monomer from reacting in the air, the tail of the dropping tube should extend below the liquid level of the ammonium ferrous sulfate aqueous solution during the dropwise addition), so as to prepare the grafting solution.
In the preparation stage of the PVDF membrane, PVDF with a pore diameter of 0.1 mu m and non-woven fabric support is cut into a membrane with the size of 10cm multiplied by 10cm, is washed by deionized water and is soaked in the deionized water for 24 hours. The clean PVDF membrane was then placed in an irradiation tube, and 200mL of the grafting solution was added to the irradiation tube. The radiant tube was sealed with vaseline and purged with nitrogen for 30min to completely remove the air from the radiant tube. Finally, the radiation tube soaked with PVDF is placed in a radiation field, the radiation dose rate is set to be 5kGy/h, the radiation time is set to be 10h, and finally, the grafted PVDF membrane is obtained and is marked as a membrane C.
Examples of the experiments
To examine the filtration capacity of the membrane, pure water and a 1g/L BSA solution prepared from 0.1mol of phosphate buffer solution were filtered by circulation using a terminal filtration apparatus. The test was provided by a nitrogen cylinder, with the test pressure set at 0.1 Mpa. According to the test results, the water flux of membrane a, membrane B and membrane C is higher when filtering the BSA solution than when filtering pure water, the percentage increase in water flux being: film A, improved by 20%; film B, improved by 30%; membrane C, 50% improvement.
In addition, the present inventors tested the effect of grafting different monomers on the performance of a polymer separation membrane according to the preparation method of example 1, including: n-vinylpyrrolidone, hydroxyethyl acrylate, acetamide glycolate, sulfopropyl methacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, allylphosphonic acid, styrenesulfonic acid. When the above monomers were grafted, the anti-fouling performance was improved to various degrees compared to the unmodified membrane, however, the water flux when filtering an aqueous BSA solution was smaller than that when filtering pure water.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of an anti-pollution high-flux modified polymer separation membrane is characterized by comprising the following steps:
adding acrylic acid monomers into the ammonium ferrous sulfate aqueous solution to prepare a grafting solution; and (3) putting the polymer separation membrane into the grafting solution, introducing inert gas to remove oxygen, and performing electron beam radiation grafting to obtain the modified polymer separation membrane.
2. The method according to claim 1, wherein the acrylic monomer is selected from one or a combination of two of the following groups: acrylic acid, acrylamide.
3. The method according to claim 1, wherein the mass fraction of the acrylic monomer in the grafting solution is 0.5% to 10%.
4. The preparation method according to claim 1, wherein the mass fraction of the ammonium ferrous sulfate in the aqueous solution of ammonium ferrous sulfate is 0.1-0.3%;
preferably, the ferrous ammonium sulfate solution is prepared according to the following steps: adding ammonium ferrous sulfate into deionized water, and ultrasonically stirring until the ammonium ferrous sulfate is completely dissolved.
5. The method according to claim 1, wherein when the acrylic monomer is added to the aqueous solution of ferrous ammonium sulfate, the tail of a dropping tube containing the acrylic monomer is extended below the liquid level of the aqueous solution of ferrous ammonium sulfate and dropped.
6. The method of claim 1, wherein the polymeric separation membrane is further pretreated by: sequentially leaching and soaking the polymer separation membrane by using deionized water;
preferably, the soaking time is 18-48 h.
7. The preparation method according to claim 1, wherein the electron beam irradiation grafting is performed at a radiation dose rate of 1.0 to 5.0kGy/h and a radiation time of 8 to 12 h;
preferably, the electron beam radiation is grafted to Co 60Radiation grafting or Cs137And (4) radiation grafting.
8. The method of claim 1, wherein the inert gas is nitrogen or argon; the time for introducing the inert gas is 20-30 min.
9. The method of claim 1, wherein the polymer separation membrane is a polyvinylidene fluoride membrane, a polysulfone membrane, a polyethylene membrane, a polypropylene membrane, a polytetrafluoroethylene membrane, a polyethersulfone membrane, or a polyamide membrane.
10. An anti-fouling, high-flux modified polymer separation membrane prepared by the method of any one of claims 1 to 9.
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