CN1261197C - Hollow fiber ultrafiltration membrane of polysulfone with permanent hydrophilicity and its preparing process - Google Patents
Hollow fiber ultrafiltration membrane of polysulfone with permanent hydrophilicity and its preparing process Download PDFInfo
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- CN1261197C CN1261197C CN 200410016118 CN200410016118A CN1261197C CN 1261197 C CN1261197 C CN 1261197C CN 200410016118 CN200410016118 CN 200410016118 CN 200410016118 A CN200410016118 A CN 200410016118A CN 1261197 C CN1261197 C CN 1261197C
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- polyvinylpyrrolidone
- oxidant
- milipore filter
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- film
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- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims description 12
- 238000000108 ultra-filtration Methods 0.000 title abstract description 9
- 239000012528 membrane Substances 0.000 title description 20
- 239000012510 hollow fiber Substances 0.000 title description 8
- 239000000835 fiber Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000001891 gel spinning Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000007800 oxidant agent Substances 0.000 claims description 23
- 230000001590 oxidative effect Effects 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 235000019394 potassium persulphate Nutrition 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract 2
- 239000003651 drinking water Substances 0.000 abstract 1
- 235000020188 drinking water Nutrition 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000009472 formulation Methods 0.000 abstract 1
- 239000010842 industrial wastewater Substances 0.000 abstract 1
- 239000010841 municipal wastewater Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000011282 treatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 230000004907 flux Effects 0.000 description 15
- 238000009987 spinning Methods 0.000 description 15
- 238000009738 saturating Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000010148 water-pollination Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- -1 trimethylammonium Chemical compound 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to a hollow polysulphone fiber ultrafiltration film with permanent hydrophilicity, and a manufacturing method thereof. The present invention is characterized in that 2 to 6% of a mixture of polyvinylpyrrolidone K-15 and K-30 is added to the usual formulation of a hollow polysulphone fiber ultrafiltration film, the proportion of K-15: K-30 is from 1:3 to 3:1; under conventional operating conditions, a hollow polysulphone fiber ultrafiltration film of which the inner diameter is from 0.7mm to 2.0mm is manufactured through dry-wet spinning technology; the film is soaked in water for 4h, and then is put in a tubular type high pressure reactor which comprises an oxydant to make polyvinylpyrrolidone fully oxidized and crosslinked; the film is put in a baking oven of 105 DEG C to be dried for more than 8h; the film is taken out and cooled to a room temperature, and the hollow polysulphone fiber ultrafiltration film still has favorable hydrophilicity. The product of the present invention has wide application in industrial wastewater treatment, municipal wastewater treatment, drinking water treatment, extraction and purification in medicinal industry, etc.
Description
One, technical field:
The present invention relates to a kind of polymeric membrane and manufacture method thereof, particularly disclose a kind of polysulfone hollow fibre milipore filter and manufacture method thereof with permanent hydrophilic.
Two, background technology:
Polysulfones has good physics and chemical property, hollow fiber ultrafiltration membrane with its preparation not only has good water permeability and stalling characteristic, but also has excellent mechanical intensity, acid and alkali-resistance, heat-resisting, anti-bacterium and microbial attack, chemicals-resistant, the anti-oxidant premium properties that waits is one of membrane material of using always.Unique deficiency is its strong hydrophobicity, reaches 74.5 °-77.0 ° with the contact angle of water, and this has seriously limited its application.People carry out modification to it by every means, and managing of having makes its sulfonation, is with-OS
3 -The negative electrical charge group, what have makes it quaternized, is with-NH
3 +Positive electrochemical lotus group.But these handle the character that has all changed polysulfones, and they have not been the PS membrane on the pure meaning, and, because preparation the time need be used the sulfonating agent of high concentration, chloromethyl ether, carcinogens such as trimethylammonium, preparation condition are very abominable, so have only a few experiments chamber product so far.Add to be with and under most conditions, make that film is easier to be polluted behind the charged group on the contrary, so chargedization is not to make the good method of resistant to pollution permanent hydrophilic PS membrane, many people transfer to adopt and make PS membrane have interim hydrophilic measure: add water-soluble high-molecular compound in casting solution (spinning solution), hydrophilic component such as surfactant, always having part in the washing process of film is retained in the film, make film have interim hydrophily, or film immersion at ethanol, in alcoholic solution such as glycerine or the surfactant solution, carry out that hygrometric state is preserved or half hygrometric state is preserved.Because what provisional hydrophiling measure was adopted all is some water-soluble substanceses, in the use of film, can lose very soon or lose gradually, PS membrane finally can recover its intrinsic hydrophobic property.Although such film initial water flux is quite big, but because its anti-fouling performance is poor, the permeation flux of film descends very soon, and such film is in case dry, will lose its most water permeability, flux is almost nil under the routine operation pressure of 0.1-0.3MPa.The assembly that is assembled into by such film has often been filled the aqueous solution of protective agent and anticorrisive agent.This has not only increased the weight of transportation greatly, and use and store in all must be very careful, must not allow its drying.
How to make PS membrane have permanent hydrophilic character? it is the target that various countries film scientific worker lays siege to always.Except chargedization of saying previously, making alloy film with SPSF also is an approach, but still keeps away the shortcoming that unavoidable charged membrane faces.The hydroaropic substance of band thiazolinyls such as acrylic acid, acrylamide, vinylpyrrolidone is grafted on the PS membrane base material, is another feasible solution route.But the method that grafting is used must be used some special equipment as radiation exposure method, uv irradiation method and plasma modification method etc., and this is not arriving of doing of general manufacturer.Japanese patent laid-open 7-155573 number (November 30 1993 date of application, approved date is June 20 nineteen ninety-five) introduced a kind of method that makes the ps hollow fiber uf membrane permanent hydrophilicization: the polyvinylpyrrolidone that in the polysulfones spinning solution, adds about 0.1-10% (weight ratio), after obtaining hollow-fibre membrane with the dry-wet spinning of routine, place distilling kettle, handle more than 5 minutes in the heated in water solution more than 110 ℃, just obtained the PS membrane of permanent hydrophilic.What this patent adopted is a kind of polyvinylpyrrolidone product, molecular weight is 10000 (K-15)-1200000 (K-90), weight ratio in spinning solution is 0.1-10%, be preferably 0.1-6%, the temperature of cross-linking reaction is more than 110 ℃, be preferably in about 121 ℃, the time of high-temperature cross-linking reaction is more than 5 minutes, is preferably in about 15-60 minute.China is domestic does not see that so far similar products production is arranged, and does not see the article report of publishing yet.
Three, summary of the invention:
Technical problem to be solved by this invention is, makes polysulfones hollow fiber ultrafiltration film have permanent hydrophilic, and this film still has excellent hydrophilic behind oven drying, and rehydration still has good pure water flux after handling.According to our research, the resulting effect of polyvinylpyrrolidone of only adding a kind of molecular weight in common polysulfones hollow fiber ultrafiltration film spinning solution is also bad, especially add this ultra high molecular weight polyethylene pyrrolidones as K-90, its addition is higher slightly, it is very big that the viscosity of spinning solution will become, and must reduce the content of membrane material (polysulfones), otherwise just be difficult for spinning, even improve the inadequate spinning of way of spinning temperature, the performance of gained film also poor (pure water flux is lower); The consumption of K-90 is very few, and the hydrophily effect is just bad.
The present invention realizes like this, a kind of polysulfone hollow fibre milipore filter with permanent hydrophilic, in the common prescription of polysulfone hollow fibre milipore filter, add the water-soluble high-molecular compound polyvinylpyrrolidone, it is characterized in that: also contain oxidant, the percentage by weight that each several part is formed is a polysulfones 16～18%; Polyethylene glycol 10%; Polyvinylpyrrolidone 4～6%; Oxidant concentration is 0.01～1%; All the other are dimethyl formamide, and described polyvinylpyrrolidone is the mixture of the K-30 of the K-15 of mean molecule quantity 10,000 and mean molecule quantity 40,000, and the ratio of K-15 and K-30 is 1: 3～3: 1.Described oxidant is potassium peroxydisulfate K
2S
2O
8Or ammonium persulfate (NH
4)
2S
2O
8It is potassium peroxydisulfate, the polyethylene glycol 10% of concentration 0.1% that formula for a product can be selected polysulfones 18%, polyvinylpyrrolidone 4%, oxidant, and all the other are dimethyl formamide.It is potassium peroxydisulfate, the polyethylene glycol 10% of concentration 0.1% that formula for a product can be selected polysulfones 16%, polyvinylpyrrolidone 6%, oxidant, and all the other are dimethyl formamide.A kind of polysulfone hollow fibre milipore filter manufacture method with permanent hydrophilic, it is characterized in that: in the common prescription of polysulfone hollow fibre milipore filter, add the water-soluble high-molecular compound polyvinylpyrrolidone, operating condition is routinely made the polysulfone hollow fibre milipore filter that internal diameter is 0.7mm～2.0mm with dry-wet spinning technology, through in water behind the 4h washing by soaking, place the tubular type high-pressure reactor that contains oxidant, the heating certain hour, carry out the high-temperature oxydation cross-linking reaction, film is placed more than 105 ℃ of dry 8h-of baking oven, taking-up is cooled to room temperature, makes the polysulfone hollow fibre milipore filter have permanent hydrophilic.The polyvinylpyrrolidone that adopts is the mixture of K-15 and K-30, and the ratio of K-15 and K-30 is 1: 3～3: 1.Also used oxidant in the prescription, concentration is 0.01～10%, and used oxidant is potassium peroxydisulfate or ammonium persulfate, and the concentration of oxidant depends on the quantity of handled polysulfones at the hollow fiber milipore filter.Used cross-linking reaction temperature is 105 ℃～120 ℃, and the time of high-temperature oxydation cross-linking reaction is 10～30 minutes.
The mixture that adds K-15 and K-30 is the most desirable, and the ratio of K-15 and K-30 is 1: 3～3: 1, and the addition of mixture is 2～6% to be advisable, and addition is low excessively, then causes the pure water flux after the dry film rehydration lower owing to hydrophily is relatively poor; Addition is too high, then may be owing to stay that polyvinylpyrrolidone in the film too much can block fenestra thereby pure water flux is not high yet, cross-linking reaction preferably has oxidant to participate in, suitable oxidant has potassium peroxydisulfate and ammonium persulfate, its concentration should be determined according to the quantity of pending hollow-fibre membrane, and is general in 0.01～10% scope.After oxidant had been arranged, the temperature of cross-linking reaction can reduce, and got final product at 105 ℃-120 ℃.10～30 minutes time of crosslinked reflection, the polysulphone super-filter membrane of gained.Even through fully dry more than the 8h, also still have good hydrophilicity in 105 ℃ baking oven, directly rehydration is handled the back and record pure water flux at 200～400l/m under the saturating film pressure of 0.1MPa
2About h.The inventive method also is suitable for polyether sulfone hollow fiber ultrafiltration membrane and the microporous barrier of making permanent hydrophilic, and the latter is the main film of using of dialyzer.
Beneficial effect of the present invention is: owing to used oxidant, cross-linking reaction just to be easy to realize that reaction temperature can obviously reduce, and by more than 110 ℃, is reduced to 105 ℃～110 ℃ and gets final product; Reaction time obviously shortens, and gets final product in 10～30 minutes.Owing to the oxidant that uses, can use the polyvinylpyrrolidone K-90 of super high molecular weight.K-90 not only is difficult to buy at home, and content is difficult to grasp in reaction system, and content is high slightly, and owing to spinning fluid viscosity can not spin silk too greatly, content is low slightly, and then the hydrophily effect of product is just bad.
Use the mixture of K-15 and K-30, ratio is 1: 3～3: 1, and consumption is 2～6%, and this is not have in the prior art.Adopt such additive, original formula of casting changed few, adopt existing spinning-drawing machine, the polysulfones raw material that China is homemade, just can adopt this technology obtain water flux greatly, the polysulfone hollow fibre milipore filter of permanent hydrophilic.
Four, the specific embodiment:
Embodiment 1:
In that (homemade or BASF produces by 18% polysulfones, inherent viscosity 0.58～0.6) in the common spinning solution that 10% polyethylene glycol (PEG400) and 72% dimethyl formamide are formed, the mixture that adding 4% is made up of with 2: 1 ratio K-15/K-30, under the operating condition of routine, be used for wet spinning, obtain internal diameter and be 0.9 millimeter, wall thickness and be 0.25 millimeter hollow-fibre membrane, this film silk soaks in water, wash after 4 hours and take out, control solid carbon dioxide branch is placed in the tubular type high-pressure reactor, wherein contains the K of 0.1% concentration
2S
2O
8Solution, reactor heating make its water temperature reach 110 ℃ rapidly, are incubated 20 minutes and promptly lower the temperature.After treating that water temperature is reduced to below 50 ℃, open reactor and take out filament, airing is placed on dry 8h in 105 ℃ the baking oven.Direct rehydration is that to record its pure water flux be 250l/m to 0.1MPa in saturating film pressure
2.h.
Embodiment 2:
Polysulfones content in the spinning solution is changed into 16% by 18%, and the ratio of K-15/K-30 is should be 1: 3 by 2: 1, and all the other are with embodiment 1.After the direct rehydration of dry film, recording, is that its pure water flux of 0.1MPa is 310l/m in saturating film pressure
2H.
Embodiment 3:
The percetage by weight of the mixture of the K-15/K-30 that adds in the spinning solution is brought up to 6% by 4%, is the ratio of K-15/K-30 should be 3: 1 by 2: 1, and all the other are with embodiment 1.After the direct rehydration of dry film, recording, is that its pure water flux of 0.1MPa is 200l/m in saturating film pressure
2.h.
Comparative example 1:
In the common spinning solution of forming by 18% polysulfones, 10% polyethylene glycol (PEG400) and 72% dimethyl formamide (DMF), under the operating condition of routine, with same spinning plate spinning, obtaining internal diameter is that 0.9 millimeter wall thickness is 0.25 millimeter a ps hollow fiber uf membrane, this film silk is soaked in water, washing is taken out behind the 4h, is that to record its pure water flux be 150l/m to 0.1MPa in saturating film pressure
2H.Equally another part of this film is soaked in water, washing is taken out behind the 4h, and airing is placed on dry 8h in 105 ℃ the baking oven.Direct rehydration is that to record its pure water flux be zero to 0.1MPa in saturating film pressure.
Comparative example 2:
Tubular reactor is contained the K of 0.1% concentration
2S
2O
8Solution changes into and contains water, and all the other are with embodiment 1.The direct rehydration of dry film is that 0.1MPa records its pure water flux and only is 10l/m in saturating film pressure
2.h.
Claims (4)
1. polysulfone hollow fibre milipore filter with permanent hydrophilic, in the common prescription of polysulfone hollow fibre milipore filter, add the water-soluble high-molecular compound polyvinylpyrrolidone, it is characterized in that: contain oxidant, described oxidant is potassium peroxydisulfate or ammonium persulfate, and the percentage by weight that polysulfone hollow fibre milipore filter prescription is formed is a polysulfones 16～18%; Polyethylene glycol 10%; Polyvinylpyrrolidone 4～6%; Oxidant concentration is 0.01～1%; All the other are dimethyl formamide, and described polyvinylpyrrolidone is the mixture of the K-30 of the K-15 of mean molecule quantity 10,000 and mean molecule quantity 40,000, and the ratio of K-15 and K-30 is 1: 3～3: 1.
2. the polysulfone hollow fibre milipore filter with permanent hydrophilic according to claim 1 is characterized in that: polysulfones 18%, polyvinylpyrrolidone 4%, oxidant are potassium peroxydisulfate, the polyethylene glycol 10% of concentration 0.1%, and all the other are dimethyl formamide.
3. the polysulfone hollow fibre milipore filter with permanent hydrophilic according to claim 1 is characterized in that: polysulfones 16%, polyvinylpyrrolidone 6%, oxidant are potassium peroxydisulfate, the polyethylene glycol 10% of concentration 0.1%, and all the other are dimethyl formamide.
4. one kind by any polysulfone hollow fibre milipore filter manufacture method with permanent hydrophilic in claim 1 or 2 or 3, it is characterized in that: in the common prescription of polysulfone hollow fibre milipore filter, add the water-soluble high-molecular compound polyvinylpyrrolidone, also adopt oxidant, described oxidant is potassium peroxydisulfate or ammonium persulfate, and the percentage by weight that polysulfone hollow fibre milipore filter prescription is formed is a polysulfones 16～18%; Polyethylene glycol 10%; Polyvinylpyrrolidone 4～6%; Oxidant concentration is 0.01～1%; All the other are dimethyl formamide; Described polyvinylpyrrolidone is the mixture of K-15 and K-30, and the ratio of K-15 and K-30 is 1: 3～3: 1; Operating condition is routinely made the polysulfone hollow fibre milipore filter that internal diameter is 0.7mm～2.0mm with dry-wet spinning technology, through in water behind the 4h washing by soaking, place the tubular type high-pressure reactor that contains oxidant, heating used cross-linking reaction temperature is 105 ℃～120 ℃, the time of high-temperature oxydation cross-linking reaction is 10～30 minutes, after carrying out the high-temperature oxydation cross-linking reaction, film is placed more than 105 ℃ of dry 8h of baking oven, taking-up is cooled to room temperature, makes the polysulfone hollow fibre milipore filter have permanent hydrophilic.
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|---|---|---|---|
| CN 200410016118 CN1261197C (en) | 2004-02-04 | 2004-02-04 | Hollow fiber ultrafiltration membrane of polysulfone with permanent hydrophilicity and its preparing process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012035402A1 (en) | 2010-09-14 | 2012-03-22 | Council Of Scientific & Industrial Research | High flux hollow fiber ultrafiltration membranes and process for the preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386136C (en) * | 2006-01-17 | 2008-05-07 | 亚美滤膜（南通）有限公司 | Production method of porous semi-permeable filter membrane |
| CN107754618A (en) * | 2017-08-28 | 2018-03-06 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of novel lasting hydrophily polysulphone super-filter membrane |
| CN111001316A (en) * | 2020-01-02 | 2020-04-14 | 李友来 | Ultrafiltration membrane, preparation method thereof, super-hydrophilic treatment method thereof and water purification equipment |
| CN113368704A (en) * | 2021-05-14 | 2021-09-10 | 科威天使环保科技集团股份有限公司 | High-performance ultrafiltration membrane for wastewater treatment and preparation method thereof |
| CN115715938A (en) * | 2022-11-30 | 2023-02-28 | 德蓝水技术股份有限公司 | Temperature-resistant alkali-resistant ultrafiltration membrane and preparation method thereof |
| EP4674515A1 (en) * | 2024-07-03 | 2026-01-07 | Elantas GmbH | Polymer solutions for the preparation of polymer membranes |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012035402A1 (en) | 2010-09-14 | 2012-03-22 | Council Of Scientific & Industrial Research | High flux hollow fiber ultrafiltration membranes and process for the preparation thereof |
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