CN104548969A - Method for preparing anti-pollution polysulfone porous membrane by self-assembling immobilization of metal ions - Google Patents
Method for preparing anti-pollution polysulfone porous membrane by self-assembling immobilization of metal ions Download PDFInfo
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- CN104548969A CN104548969A CN201310473128.5A CN201310473128A CN104548969A CN 104548969 A CN104548969 A CN 104548969A CN 201310473128 A CN201310473128 A CN 201310473128A CN 104548969 A CN104548969 A CN 104548969A
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Abstract
The invention relates to a method for preparing an anti-pollution polysulfone porous membrane by self-assembling immobilization of metal ions. According to surface electrical load properties of a membrane prepared from a polysulfone material, an amino-containing compound with high positive charge density and hydrophily is used as a modification material, the modification material is adsorbed by the surface of the polysulfone porous membrane under electrostatic interaction, through a large amount of amino groups of the modification material, the modification material and Cu<2+>, Zn<2+> or Ag<+> of an inorganic antibacterial agent undergo a coordinated complexation reaction, and the inorganic antibacterial agent is immobilized on the modification material molecule by complexation action so that the polysulfone porous membrane with good hydrophily and antibacterial activity is obtained. The prepared polysulfone porous membrane has hydrophily, antibacterial property and pollution resistance. The method has simple processes, does not need complex equipment and is suitable for industrial scale application. The porous membrane can be widely used in water treatment in the field of environment, chemical engineering, foods and medicine.
Description
Technical field
The present invention relates to the preparation technology of antibacterial polysulfones perforated membrane, is a kind of method that self assembly supported metal ion prepares antipollution polysulfones perforated membrane specifically.
Background technology
Along with the aggravation of environmental pollution and the exhaustion of resource, the cry of people to the cycling and reutilization of water and advanced treating is more and more higher with requirement.Membrane separation technique is described as the technology of 21 century, is widely applied in water treatment field such as wastewater treatment and reuse, ultra-pure water production, water conditioning boiler, municipal sewage treatment, desalinization, brackish water desalination, municipal water supplies.As the efficient isolation technics of one, although membrane separation technique has been people's common concern, there is membrane pollution problem when it is applied to suitability for industrialized production, membrane pollution problem not only makes the permeability decrease of film, and make film that deterioration, damage film occur, finally cause shorten the service life of film.For micro-filtration conventional in industrial production and ultra-filtration process, fouling membrane is just larger on the impact of the latter, and there are some researches show, before and after Pollution of Ultrafiltration Membrane, pure water flux is compared and can be reduced by the 20% even reduction by 40% had.
The character of pollutant and the speed of pollution relevant with Water Supplies, different pollutants can cause infringement in various degree to membrane element capability.Membrane biological pollution usually wants problems faced in water treatment by membrane, always has a large amount of microorganisms in surface water or waste water, and they can utilize the inorganic substances in water body and organic substance to carry out the amount reproduction of self under appropriate conditions.Because biological pollution is lived, therefore be characterized in, once form pollutant in membrane module front end, just probably expanding in whole system, all producing very ill effect to whole membranous system.
Bacteriostatic agent by interference, destroy physiology, biochemical reaction and the metabolic activity relevant to microbial cell, make the impaired or protoplast disintegration of cell membrane, reach the effect that microorganism is even killed in suppression, bacteriostatic agent is divided into organic bacteriostatic agent and inorganic bacteriostatic agent.Destroy cell membrane by chemical reaction organic bacteriostatic agent (as polypyridine salt and polyquaternium etc.), make protein denaturation, metabolism is obstructed, thus play the effects such as sterilization, anticorrosion and mildew-resistant, organic bacteriostatic agent sterilizing speed is fast, but have that preparation condition complexity, stability and poor compatibility, safety in utilization are poor, the shortcoming such as poor heat resistance, facile hydrolysis, service life are short.Inorganic bacteriostatic agent comprises metal cation component (as metal cation components such as argentiferous, zinc, copper) and inorganic carrier (as zeolite, phosphate etc.), they make antibacterial to be long-lastingly improved by slow releasing, inorganic bacteriostatic agent have has a broad antifungal spectrum, good heat resistance, security high, do not produce the advantages such as drug resistance for a long time, be applied widely in recent years, if by argentiferous (Ag
+), zinc (Zn
2+), copper (Cu
2+) etc. the inorganic bacteriostatic agent of metal cation component be incorporated in the preparation process of polysulfones perforated membrane, the polysulfones perforated membrane of preparation will obtain antibacterial functions, and the anti-fouling performance of film can be made to be improved.
Polysulfones macromolecular material (comprising polysulfones, polyether sulfone, polyether-ketone etc.) has cheap and easy to get, good mechanical strength, creep resistant, the close property of resistance to compression is good, and the advantage such as chemical stability, heat resistance, acid and alkali-resistance, chlorine resistance be good and anti-oxidant, it is the filming polymer of excellent performance, polysulfones perforated membrane ultra-filtration process because separation is large, operating temperature in room temperature up and down, equipment and the feature such as simple to operate, very active in the application and development of water treatment, waste water control and biotechnology field.But polysulfones is hydrophobicity high polymer, easily causes fouling membrane, the service life of film is shortened, production cost increase.
Patent CN1683061 discloses a kind of nano antiseptic material-polysulphone composite microporous filter film and preparation method thereof, by nano titanium oxide, Nano Silver, Nano-Zinc and Nanometer Copper, wherein one or more carry out mixing interpolation to the method, enhance the contamination resistance of film, and the hydrophily of film and permeability are improved, but nano material is difficult to be uniformly dispersed in casting solution, the quality of the prepared film of impact and performance.
Patent CN201110442062.4 describes a kind of antimicrobial polysulphone flat ultrafiltration membrane and preparation method thereof, be difficult to be uniformly dispersed for nano material, and need to carry out pretreated shortcoming, take polysulfones as filmogen, the nano silver particles obtained with liquid-phase reduction silver nitrate method is for antibacterial additives, adopt Nano Silver-polysulfones composite flat ultrafiltration membrane prepared by immersion precipitation phase inversion process, but need other reducing agent additional to reduce with obtained Nano Silver to silver nitrate, and need to readjust parameters of preparation, add the complexity of technical process.
In order to the heat resistance of polysulfones material of preparing, chemical resistance and the advantage such as mechanical strength preferably should be kept, overcome its shortcoming that is hydrophobic, that easily cause fouling membrane again, film surface is made to have certain hydrophily, also to consider the Cost Problems of masking, in the preparation process of polysulfones perforated membrane, carry out surface modification to existing membrane material is a kind of simple and easy to do film-forming method, is also the focus of current membrane material and masking technique research.
Summary of the invention
For the defect existed in prior art, a kind of self assembly supported metal ion is the object of the present invention is to provide to prepare the method for antipollution polysulfones perforated membrane, the polysulfones perforated membrane prepared has hydrophilic antimicrobial performance, contamination resistance is strong, equipment without the need to complexity simple to operate, is suitable for industrial scale applications.Prepared perforated membrane can be widely used in the water treatment procedure of environment, chemical industry, food, medicine and other fields.
For reaching above object, the technical scheme that the present invention takes is:
A kind of self assembly supported metal ion prepares the method for antipollution polysulfones perforated membrane, it is characterized in that: when carrying out hydrophilic, antibacterial modified to polysulfones porous film surface, the character of the film surface bear electricity utilizing polysulfones material to make, select high, the tool hydrophily of positive charge density and in molecular structure containing amino compound as material modified, pass through self-assembling technique, polysulfones porous film surface is adsorbed in by electrostatic interaction by material modified, recycle in material modified molecule and contain a large amount of amino, make the Cu in material modified and inorganic bacteriostatic agent
2+, Zn
2+or Ag
+generation ligand complex reacts, and inorganic bacteriostatic agent is immobilized on material modified molecule by complexing, and then prepares the polysulfones perforated membrane with good hydrophilic and bacteriostasis property.
On the basis of technique scheme, specifically comprise the following steps:
1) take the modified compound that mass percentage concentration is 1% ~ 10%, be dissolved in deionized water and be made into the uniform modified compound aqueous solution;
2) polysulfones perforated membrane is placed in the above-mentioned modified compound aqueous solution and at least soaks 12 ~ 24 hours, low rate mixing while immersion, carry out Electrostatic Absorption self assembly;
3) with the polysulfones perforated membrane that deionized water oscillation cleaning has soaked, removed by the modified compound molecule of film excess surface, the polysulfones perforated membrane after cleaning dries for subsequent use;
4) prepare the inorganic bacteriostatic agent that mass percentage concentration is 1% ~ 10%, described inorganic bacteriostatic agent is metal ion Cu
2+, Zn
2+or Ag
+soluble salt solutions, be immersed in wherein by drying polysulfones perforated membrane for subsequent use, low rate mixing, carries out ligand complex with modified compound and reacts 4 to 12 hours, formed chelate make metal ion immobilized in polysulfones porous film surface;
5) metal ion that ligand complex reacted polysulfones perforated membrane deionized water vibration washing surface is unnecessary, being kept at mass percentage concentration is that in the glycerine water solution of 20%, immersion guarantor hole is for subsequent use.
On the basis of technique scheme, described modified compound is the mixture of any one or two or more any proportioning in polylysine, polymine, water soluble chitosan, chitosan oligosaccharide, monoethanolamine, arginine, lysine, histidine.
On the basis of technique scheme, described polysulfones perforated membrane is hollow-fibre membrane or Flat Membrane.
On the basis of technique scheme, the membrane material of described polysulfones perforated membrane is the mixture of any one or two or more any proportioning in polysulfones, polyether sulfone, SPSF, sulfonated polyether sulfone, polyether-ketone, benzodiazine polyethersulfone ketone.
On the basis of technique scheme, described metal ion Cu
2+, Zn
2+or Ag
+soluble salt solutions be: Cu
2+acetic acid, nitric acid, hydrochloric acid or sulfuric acid solution; Or be Zn
2+acetic acid, nitric acid, hydrochloric acid or sulfuric acid solution; Or be Ag
+salpeter solution.
Self assembly supported metal ion of the present invention prepares the method for antipollution polysulfones perforated membrane, and the polysulfones perforated membrane prepared has hydrophilic antimicrobial performance, and contamination resistance is strong, and the equipment without the need to complexity simple to operate, is suitable for industrial scale applications.Prepared perforated membrane can be widely used in the water treatment procedure of environment, chemical industry, food, medicine and other fields.
Detailed description of the invention
Self assembly supported metal ion of the present invention prepares the method for antipollution polysulfones perforated membrane, carrying out hydrophilic to polysulfones porous film surface, time antibacterial modified, the character of the film surface bear electricity made according to polysulfones material is (see the milipore filter characteristic research of hyperfiltration treatment alkaline straw-pulp black liquid, Xi'an Mining Technology Inst journal, 1992, 19(1): 5-8), core concept of the present invention is: select positive charge density high, tool hydrophily (hydrophily is strong) and compound containing amino (containing a large amount of amino in molecular structure) in molecular structure are as material modified (membrane surface modification material, modified compound), pass through self-assembling technique, polysulfones porous film surface is adsorbed in by electrostatic interaction by material modified, recycle in material modified molecule containing a large amount of amino, make the Cu in material modified and inorganic bacteriostatic agent
2+, Ag
+or Zn
2+generation ligand complex reacts, and inorganic bacteriostatic agent is immobilized on material modified molecule by complexing, and then prepares the polysulfones perforated membrane with good hydrophilic and bacteriostasis property, makes the raising that the antifouling property of polysulfones perforated membrane obtains by a relatively large margin.
On the basis of technique scheme, specifically comprise the following steps:
1) take the modified compound that mass percentage concentration is 1% ~ 10%, be dissolved in deionized water and be made into the uniform modified compound aqueous solution;
2) polysulfones perforated membrane is placed in the above-mentioned modified compound aqueous solution and at least soaks 12 ~ 24 hours, low rate mixing while immersion, carry out Electrostatic Absorption self assembly;
3) with the polysulfones perforated membrane that deionized water oscillation cleaning has soaked, removed by the modified compound molecule of film excess surface, the polysulfones perforated membrane after cleaning dries for subsequent use;
4) prepare the inorganic bacteriostatic agent that mass percentage concentration is 1% ~ 10%, described inorganic bacteriostatic agent is metal ion Cu
2+, Zn
2+or Ag
+soluble salt solutions, be immersed in wherein by drying polysulfones perforated membrane for subsequent use, low rate mixing, carries out ligand complex with modified compound and reacts 4 to 12 hours, formed chelate make metal ion immobilized in polysulfones porous film surface;
5) metal ion that ligand complex reacted polysulfones perforated membrane deionized water vibration washing surface is unnecessary, being kept at mass percentage concentration is that in the glycerine water solution of 20%, immersion guarantor hole is for subsequent use.
On the basis of technique scheme, described modified compound is the mixture of any one or two or more any proportioning in polylysine, polymine, water soluble chitosan, chitosan oligosaccharide, monoethanolamine, arginine, lysine, histidine.
On the basis of technique scheme, the membrane material of described polysulfones perforated membrane is the mixture of any one or two or more any proportioning in polysulfones, polyether sulfone, SPSF, sulfonated polyether sulfone, polyether-ketone, benzodiazine polyethersulfone ketone; Described polysulfones perforated membrane (commercially available prod) is hollow-fibre membrane or Flat Membrane, preferred flat plate ultrafiltration membrane.
On the basis of technique scheme, described metal ion Cu
2+, Zn
2+or Ag
+soluble salt solutions be: Cu
2+acetic acid, nitric acid, hydrochloric acid or sulfuric acid solution; Or be Zn
2+acetic acid, nitric acid, hydrochloric acid or sulfuric acid solution; Or be Ag
+salpeter solution.
Any one in above-mentioned soluble salt solutions, preferred Cu
2+solubility Acetate Solution or Zn
2+solubility Acetate Solution or Ag
+nitrate solution.
The present invention has the following advantages:
1) the present invention uses self-assembling technique to carry out modification to polysulfones porous film surface, select that high, the hydrophily of positive charge density is strong, in molecule containing a large amount of amino compound as modifier, utilize the method for Electrostatic Absorption, ligand complex by hydrophilic compound and to have the metal ion of bacteriostasis immobilized on film surface, make polysulfones perforated membrane have hydrophilic and antibacterial dual anti-pollution simultaneously, significantly improve the antifouling property of film, extend the service life of film, reduce the use cost of film;
2) modifier is again through complexing of metal ion after Electrostatic Absorption, and adjacent modifier molecules long-chain can be interconnected by the crane span structure effect of metal ion, difficult drop-off, the modified layer of polysulfones perforated membrane is stablized, hydrophilic antimicrobial consistency of performance;
3) method of modifying of the present invention does not produce a very large impact the mechanical property of polysulfones perforated membrane and heat resistance, can not cause the fracture of polysulfones material of preparing backbone structure, also can not change the internal structure of perforated membrane;
4) surface modifying method of polysulfones perforated membrane of the present invention, each step operation is simple, and mild condition is easy to control, and without the need to the equipment of complexity, is applicable to the plant-scale surface modification treatment of polysulfones perforated membrane.
Be below specific embodiment, described embodiment only in order to explain the present invention, is not construed as limiting the invention, and the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
In performance measurement of the present invention, the strainability of film is characterized by pure water flux, the pure water flux by experiment outer press filtering device of the homemade dead end in room measures, be about to be cut into circular film after the polysulfones Flat Membrane is before modified dried naturally, put into ultrafiltration cup, or the polysulfones hollow-fibre membrane is before modified packaged into assembly, first precompressed 30min under 0.15Mpa, until water flux is basicly stable, then under 0.1MPa, measure the pure water flux of polysulfones perforated membrane before modified; The hydrophilicity of film is characterized by contact angle, namely with three-stage distillation water with lie drip method DSA100 contact angle instrument (
germany) contact angle is measured on; Film cutoff performance measures using the bovine serum albumin of 1g/L (BSA) solution as medium; The anti-microbial property of film characterizes by measuring the antibiotic rate of film to indicator bacteria, concrete grammar can carry out according to the Anti-microbial Performance Tests method of QB/T2591-2003 antibiotic plastic, indicator bacteria is staphylococcus aureus (Staphylococcus aureus) ATCC6538 and ETEC (Escherichia coli) ATCC25922, calculates antibiotic rate according to assay.
Embodiment 1
To choose material of preparing be the flat plate ultrafiltration membrane of polysulfones is basement membrane (main membrane parameter is in table 1), being immersed in mass percent is in the polymine deionized water solution of 5%, low rate mixing took out after 12 hours, the polymine of polysulphone super-filter membrane excess surface is washed away with deionized water vibration, drying rear immersion mass percent is in the Schweinfurt green solution of 5%, low rate mixing carries out ligand complex reaction in 6 hours, wash the metal ion of modified polysulphone super-filter membrane excess surface with deionized water vibration after taking-up, obtain the polysulphone super-filter membrane through hydrophilic antimicrobial modification, then for subsequent use with the glycerine water solution immersion guarantor hole of 20%.Modified Membrane prepared after measured and the performance parameter of basement membrane are in table 1.
Embodiment 2
To get material of preparing be the flat plate ultrafiltration membrane of polyether sulfone is basement membrane (main membrane parameter is in table 1), being immersed in mass percent is in the mixture deionized water solution of the chitosan oligosaccharide of 7% and the water soluble chitosan composition of 3%, low rate mixing took out after 24 hours, chitosan oligosaccharide and the chitosan molecule of polysulphone super-filter membrane excess surface is washed away with deionized water vibration, drying rear immersion mass percent is in the liquor argenti nitratis ophthalmicus of 10%, low rate mixing carries out ligand complex reaction in 4 hours, wash the metal ion of modified poly (ether-sulfone) ultrafiltration membrane excess surface with deionized water vibration after taking-up, obtain the poly (ether-sulfone) ultrafiltration membrane through hydrophilic antimicrobial modification, then for subsequent use with the glycerine water solution immersion guarantor hole of 20%.Modified Membrane prepared after measured and the performance parameter of basement membrane are in table 1.
Embodiment 3
To choose material of preparing be the flat plate ultrafiltration membrane of SPSF/polyether sulfone is basement membrane (main membrane parameter is in table 1), being immersed in mass percent is that in the polylysine deionized water solution of 1%, low rate mixing took out after 16 hours, the polylysine molecule of SPSF/poly (ether-sulfone) ultrafiltration membrane excess surface is washed away with deionized water vibration, drying rear immersion mass percent is in the zinc acetate solution of 3%, low rate mixing carries out ligand complex reaction in 12 hours, with the metal ion of deionized water vibration washing SPSF/poly (ether-sulfone) ultrafiltration membrane excess surface after taking-up, obtain the SPSF/poly (ether-sulfone) ultrafiltration membrane through hydrophilic antimicrobial modification, then for subsequent use with the glycerine water solution immersion guarantor hole of 20%.After measured, prepared Modified Membrane and the performance parameter of basement membrane are in table 1.
Embodiment 4
To get material of preparing be the flat plate ultrafiltration membrane of SPSF/polyether-ketone is basement membrane (main membrane parameter is in table 1), being immersed in mass percent is in the monoethanolamine deionized water solution of 3%, low rate mixing took out after 18 hours, the unnecessary ethanolamine molecules of SPSF/polyether-ketone ultrafiltration membrane surface is washed away with deionized water vibration, drying rear immersion mass percent is in the copper-bath of 4%, low rate mixing carries out ligand complex reaction in 8 hours, with the metal ion that SPSF/polyether-ketone ultrafiltration membrane surface that deionized water vibration washing is modified is unnecessary after taking-up, obtain the SPSF/polyether-ketone milipore filter through hydrophilic antimicrobial modification, then for subsequent use with the glycerine water solution immersion guarantor hole of 20%.Modified Membrane prepared after measured and the performance parameter of basement membrane are in table 1.
Embodiment 5
To choose material of preparing be the Flat Membrane of sulfonated polyether sulfone is basement membrane (main membrane parameter is in table 1), being immersed in mass percent is in the mixture aqueous solution of the arginine of 3% and the lysine composition of 5%, low rate mixing took out after 12 hours, the amino acid molecular of polysulphone super-filter membrane excess surface is washed away with deionized water vibration, drying rear immersion mass percent is in the copper chloride solution of 6%, low rate mixing carries out ligand complex reaction in 8 hours, with the metal ion that deionized water vibration washing sulfonated polyether sulfone porous film surface is unnecessary after taking-up, obtain the sulfonated polyether sulfone film through hydrophilic antimicrobial modification, then for subsequent use with the glycerine water solution immersion guarantor hole of 20%.Modified Membrane prepared after measured and the performance parameter of basement membrane are in table 1.
Embodiment 6
To choose material of preparing be the hollow fiber porous film of benzodiazine polyethersulfone ketone is basement membrane (main membrane parameter is in table 1), being immersed in mass percent is that in the histidine deionized water solution of 2%, low rate mixing took out after 12 hours, the histidine molecule of film excess surface is washed away with deionized water vibration, drying rear immersion mass percent is in the zinc nitrate solution of 1%, low rate mixing carries out ligand complex reaction in 8 hours, wash the metal ion of modified benzodiazine polyethersulfone ketone hollow-fibre membrane excess surface with deionized water vibration after taking-up, obtain the benzodiazine polyethersulfone ketone hollow fiber porous film through hydrophilic antimicrobial modification, then for subsequent use with the glycerine water solution immersion guarantor hole of 20%.Modified Membrane prepared after measured and the performance parameter of basement membrane are in table 1.
Table 1 Modified Membrane compares with the performance parameter of basement membrane
As can be seen from above embodiment and basement membrane performance test parameter, the contact angle of the polysulfones porous film surface utilizing the present invention modified all has decline in various degree, and the rejection of BSA increases, and illustrates that the hydrophily of film and strainability increase; From bacteriostatic test result, the anti-microbial property of Modified Membrane significantly promotes.Based on the above results, after self assembly supported metal ion, the contamination resistance of polysulfones Modified Membrane is greatly improved.
The content be not described in detail in this description belongs to the known prior art of professional and technical personnel in the field.
Claims (6)
1. a self assembly supported metal ion prepares the method for antipollution polysulfones perforated membrane, it is characterized in that: when carrying out hydrophilic, antibacterial modified to polysulfones porous film surface, the character of the film surface bear electricity utilizing polysulfones material to make, select high, the tool hydrophily of positive charge density and in molecular structure containing amino compound as material modified, pass through self-assembling technique, polysulfones porous film surface is adsorbed in by electrostatic interaction by material modified, recycle in material modified molecule and contain a large amount of amino, make the Cu in material modified and inorganic bacteriostatic agent
2+, Zn
2+or Ag
+generation ligand complex reacts, and inorganic bacteriostatic agent is immobilized on material modified molecule by complexing, and then prepares the polysulfones perforated membrane with good hydrophilic and bacteriostasis property.
2. self assembly supported metal ion as claimed in claim 1 prepares the method for antipollution polysulfones perforated membrane, it is characterized in that, specifically comprises the following steps:
1) take the modified compound that mass percentage concentration is 1% ~ 10%, be dissolved in deionized water and be made into the uniform modified compound aqueous solution;
2) polysulfones perforated membrane is placed in the above-mentioned modified compound aqueous solution and at least soaks 12 ~ 24 hours, low rate mixing while immersion, carry out Electrostatic Absorption self assembly;
3) with the polysulfones perforated membrane that deionized water oscillation cleaning has soaked, removed by the modified compound molecule of film excess surface, the polysulfones perforated membrane after cleaning dries for subsequent use;
4) prepare the inorganic bacteriostatic agent that mass percentage concentration is 1% ~ 10%, described inorganic bacteriostatic agent is metal ion Cu
2+, Zn
2+or Ag
+soluble salt solutions, be immersed in wherein by drying polysulfones perforated membrane for subsequent use, low rate mixing, carries out ligand complex with modified compound and reacts 4 to 12 hours, formed chelate make metal ion immobilized in polysulfones porous film surface;
5) metal ion that ligand complex reacted polysulfones perforated membrane deionized water vibration washing surface is unnecessary, being kept at mass percentage concentration is that in the glycerine water solution of 20%, immersion guarantor hole is for subsequent use.
3. self assembly supported metal ion as claimed in claim 2 prepares the method for antipollution polysulfones perforated membrane, it is characterized in that: described modified compound is the mixture of any one or two or more any proportioning in polylysine, polymine, water soluble chitosan, chitosan oligosaccharide, monoethanolamine, arginine, lysine, histidine.
4. self assembly supported metal ion as claimed in claim 2 prepares the method for antipollution polysulfones perforated membrane, it is characterized in that: described polysulfones perforated membrane is hollow-fibre membrane or Flat Membrane.
5. self assembly supported metal ion as claimed in claim 4 prepares the method for antipollution polysulfones perforated membrane, it is characterized in that: the membrane material of described polysulfones perforated membrane is the mixture of any one or two or more any proportioning in polysulfones, polyether sulfone, SPSF, sulfonated polyether sulfone, polyether-ketone, benzodiazine polyethersulfone ketone.
6. self assembly supported metal ion as claimed in claim 2 prepares the method for antipollution polysulfones perforated membrane, it is characterized in that: described metal ion Cu
2+, Zn
2+or Ag
+soluble salt solutions be: Cu
2+acetic acid, nitric acid, hydrochloric acid or sulfuric acid solution; Or be Zn
2+acetic acid, nitric acid, hydrochloric acid or sulfuric acid solution; Or be Ag
+salpeter solution.
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