CN103272496A - Method for preparing hydrophilic polyvinylidene fluoride flat sheet membrane - Google Patents
Method for preparing hydrophilic polyvinylidene fluoride flat sheet membrane Download PDFInfo
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- CN103272496A CN103272496A CN2013102493742A CN201310249374A CN103272496A CN 103272496 A CN103272496 A CN 103272496A CN 2013102493742 A CN2013102493742 A CN 2013102493742A CN 201310249374 A CN201310249374 A CN 201310249374A CN 103272496 A CN103272496 A CN 103272496A
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Abstract
The invention discloses a method for preparing a hydrophilic polyvinylidene fluoride flat sheet membrane, which comprises the following steps: 1, sequentially adding polyvinylidene fluoride resin with concentration of 12 to 30 weight percent, a pore-forming agent with concentration of 2 to 10 weight percent, organic alkali with concentration of 2 to 30 weight percent and a solvent with concentration of 50 to 80 weight percent into a reaction kettle and uniformly stirring and dissolving the raw materials to obtain film casting liquid; 2, uniformly coating the film casting liquid prepared in the step 1 on a non-woven fabric base material by a flat sheet film scraping machine; 3, soaking a flat sheet film prepared in the step 2 into 3 weight percent of potassium permanganate solution; and 4, soaking the flat sheet film processed in the step 3 into 5 weight percent of sodium hydrogen sulfite solution to obtain the hydrophilic polyvinylidene fluoride flat sheet membrane. The preparation method disclosed by the invention adopts a manner of adding the organic alkali into the film casting liquid to perform hydrophilic modification on a polyvinylidene fluoride film; the preparation method is simple to operate; and reaction conditions in each step are easy to control.
Description
Technical field
The present invention relates to a kind of preparation method of polyvinylidene fluoride flat film, be specifically related to a kind of preparation method of hydrophilicity kynoar Flat Membrane.
Background technology
Kynoar is a kind of macromolecular material of function admirable, owing to have good chemical stability, heat endurance and mechanical strength, extensively applies to fields such as ultrafiltration, micro-filtration, film distillation, gas separation membrane process as membrane material.But because the film that Kynoar is made surface can be low, present stronger hydrophobicity, easily produce adsorptivity and pollute, hindered polyvinylidene fluoride film and further applied.In recent years, the researcher is devoted to introduce various hydrophilic radicals to improve the hydrophily on polyvinylidene fluoride film surface by method of modifying at Kynoar main chain or film surface always, handling with highly basic is the effective ways that improve polyvinylidene fluoride film hydrophilically, two keys of handling the back generation have the certain reaction activity, two keys can directly carry out graft reaction, or carry out graft modification with hydrophilic monomer again after being oxidized to hydroxyl, carboxyl.
Highly basic is handled polyvinylidene fluoride film to improve its hydrophily, the reaction that mainly utilizes Kynoar to be easy to remove the hydrogen fluorine under alkali condition comes substep to carry out surface chemical modification, bibliographical information mostly is to adopt inorganic strong alkali to handle after the Kynoar film forming at present, it is additive that this method adopts the organic base polyethylene polyamine, directly be added in the casting solution, polyvinylidene fluoride film is carried out hydrophilic modification.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of hydrophilicity kynoar Flat Membrane, utilize Kynoar to be easy under alkali condition, remove the reaction of hydrogen fluorine, adopt conventional dissolving, polyvinylidene fluoride resin, pore-foaming agent, organic base are mixed in solvent, scrape membrane process by solution phase transfer flat board and prepare high flux, hydrophilicity kynoar Flat Membrane.
In order to reach above-mentioned technique effect, the present invention adopts following technical scheme, and its preparation methods steps is as follows:
Step 1. is that the polyvinylidene fluoride resin of 12-30 wt%, pore-foaming agent, the organic base of 2-30 wt%, the 50-80wt% solvent that concentration is 2-10 wt% add in the reactor successively with concentration, above-mentioned solution 40-80 ℃ following stirring and dissolving is even, and stirring reaction obtained casting solution after 24 hours.
Step 2. evenly is coated in the casting solution that step 1 makes on the non-woven fabrics base material with flat membrane casting equipment, and applied thickness is controlled about 0.2mm, and the Flat Membrane after the coating enters into water-bath and is cured, and bath temperature is controlled between 20～50 ℃.
The Flat Membrane that step 3. makes step 2 is immersed in the liquor potassic permanganate of 3 wt%, takes out behind the 30min, removes the potassium permanganate of remained on surface with deionized water.
Step 4. is handled the rear plate film with step 3 and is immersed in the solution of sodium bisulfite of 5 wt%, takes out behind the 30min, removes the sodium hydrogensulfite of remained on surface with deionized water, obtains the hydrophilicity kynoar Flat Membrane.
According to the preferred embodiment of the invention, in above-mentioned preparation method, described pore-foaming agent is one or more following mixtures: polyvinylpyrrolidone, polyethylene glycol, lithium chloride.
According to the preferred embodiment of the invention, in above-mentioned preparation method, described solvent is following a kind of: N, dinethylformamide, N, N-dimethylacetylamide, N-methyl pyrrolidone.
According to the preferred embodiment of the invention, in above-mentioned preparation method, described organic base is following a kind of: polyethylene polyamine, ethylenediamine, n-propylamine.
The present invention compared with prior art has following beneficial effect: employing is added organic base polyvinylidene fluoride film is carried out hydrophilic modification among the preparation method of the present invention in casting solution, and the preparation method is simple, and each step reaction condition is easy to control.
The specific embodiment
The invention will be further elaborated and explanation below in conjunction with embodiment.
Embodiment 1
Step 1. concentration is the polyvinylidene fluoride resin of 15 wt%, the polyethylene glycol that concentration is 5 wt%, the polyethylene polyamine of 15 wt%, the N of 65 wt%, the N-dimethylacetylamide adds in the reactor successively, 60 ℃ of following stirring and dissolving of above-mentioned solution are even, and stirring reaction obtained casting solution after 24 hours.
Step 2. evenly is coated in the casting solution that step 1 makes on the non-woven fabrics base material with flat membrane casting equipment, and applied thickness is controlled about 0.2mm, and the Flat Membrane after the coating enters into water-bath and is cured, and bath temperature is controlled to be 30 ℃.
The Flat Membrane that step 3. makes step 2 is immersed in the liquor potassic permanganate of 3 wt%, takes out behind the 30min, removes the potassium permanganate of remained on surface with deionized water.
Step 4. is handled the rear plate film with step 3 and is immersed in the solution of sodium bisulfite of 5 wt%, takes out behind the 30min, removes the sodium hydrogensulfite of remained on surface with deionized water, obtains the hydrophilicity kynoar Flat Membrane.
Prepared hydrophilicity kynoar Flat Membrane pore-forming performance is good, and fenestra is evenly distributed, and membrane aperture is 0.2 m, and the pure water flux of film is 2400L/m under 0.1MPa pressure
2H.
Embodiment 2
Step 1. concentration is that polyvinylidene fluoride resin, the concentration of 18 wt% is the polyvinylpyrrolidone of 5 wt%, concentration is the lithium chloride of 1 wt%, the ethylenediamine of 10wt%, the N of 66 wt%, dinethylformamide adds in the reactor successively, 70 ℃ of following stirring and dissolving of above-mentioned solution are even, and stirring reaction obtained casting solution after 24 hours.
Step 2. evenly is coated in the casting solution that step 1 makes on the non-woven fabrics base material with flat membrane casting equipment, and applied thickness is controlled about 0.2mm, and the Flat Membrane after the coating enters into water-bath and is cured, and bath temperature is controlled to be 45 ℃.
The Flat Membrane that step 3. makes step 2 is immersed in the liquor potassic permanganate of 3 wt%, takes out behind the 30min, removes the potassium permanganate of remained on surface with deionized water.
Step 4. is handled the rear plate film with step 3 and is immersed in the solution of sodium bisulfite of 5 wt%, takes out behind the 30min, removes the sodium hydrogensulfite of remained on surface with deionized water, obtains the hydrophilicity kynoar Flat Membrane.
Prepared hydrophilicity kynoar Flat Membrane pore-forming performance is good, and fenestra is evenly distributed, and membrane aperture is 0.45 m, and the pure water flux of film is 4500L/m under 0.1MPa pressure
2H.
Embodiment 3
Step 1. concentration is that polyvinylidene fluoride resin, the concentration of 25 wt% is the polyethylene glycol of 4 wt%, concentration is the lithium chloride of 1 wt%, the ethylenediamine of 6wt%, the N of 64 wt%, dinethylformamide adds in the reactor successively, 50 ℃ of following stirring and dissolving of above-mentioned solution are even, and stirring reaction obtained casting solution after 24 hours.
Step 2. evenly is coated in the casting solution that step 1 makes on the non-woven fabrics base material with flat membrane casting equipment, and applied thickness is controlled about 0.2mm, and the Flat Membrane after the coating enters into water-bath and is cured, and bath temperature is controlled to be 40 ℃.
The Flat Membrane that step 3. makes step 2 is immersed in the liquor potassic permanganate of 3 wt%, takes out behind the 30min, removes the potassium permanganate of remained on surface with deionized water.
Step 4. is handled the rear plate film with step 3 and is immersed in the solution of sodium bisulfite of 5 wt%, takes out behind the 30min, removes the sodium hydrogensulfite of remained on surface with deionized water, obtains the hydrophilicity kynoar Flat Membrane.
Prepared hydrophilicity kynoar Flat Membrane pore-forming performance is good, and fenestra is evenly distributed, and for separating of concentration 1g/L bovine serum albumin buffer solution, flux can maintain 240 L/m
2H, rejection is 98%.
What more than enumerate only is the specific embodiment of patent of the present invention, the invention is not restricted to above-mentioned case study on implementation, and any variation without prejudice to the patent principle is all in the protection domain of patent of the present invention.
Claims (4)
1. the preparation method of a hydrophilicity kynoar Flat Membrane is characterized in that preparation method's step is as follows:
Step 1, be that the polyvinylidene fluoride resin of 12-30 wt%, pore-foaming agent, the organic base of 2-30 wt%, the 50-80wt% solvent that concentration is 2-10 wt% add in the reactor successively with concentration, above-mentioned solution is even 40-80 ℃ of following stirring and dissolving, and stirring reaction obtained casting solution after 24 hours;
Step 2, the casting solution that step 1 is made evenly are coated on the non-woven fabrics base material with flat membrane casting equipment, and applied thickness is controlled about 0.2mm, and the Flat Membrane after the coating enters into water-bath and is cured, and bath temperature is controlled between 20～50 ℃;
Step 3, the Flat Membrane that step 2 is made are immersed in the liquor potassic permanganate of 3 wt%, take out behind the 30min, remove the potassium permanganate of remained on surface with deionized water;
Step 4, step 3 is handled the rear plate film be immersed in the solution of sodium bisulfite of 5 wt%, take out behind the 30min, remove the sodium hydrogensulfite of remained on surface with deionized water, obtain the hydrophilicity kynoar Flat Membrane.
2. according to the preparation method of the described a kind of hydrophilicity kynoar Flat Membrane of claim 1, it is characterized in that described pore-foaming agent is one or more following mixtures: polyvinylpyrrolidone, polyethylene glycol, lithium chloride.
3. according to the preparation method of the described a kind of hydrophilicity kynoar Flat Membrane of claim 1, it is characterized in that described solvent is following a kind of: N, dinethylformamide, N, N-dimethylacetylamide, N-methyl pyrrolidone.
4. according to the preparation method of the described a kind of hydrophilicity kynoar Flat Membrane of claim 1, it is characterized in that described organic base is following a kind of: polyethylene polyamine, ethylenediamine, n-propylamine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626922A (en) * | 2013-11-29 | 2014-03-12 | 内蒙古科技大学 | Method for preparing modified polyvinylidene fluoride one-step grafted 3-sulfonic acid propyl methacrylate (SPMA) proton exchange membrane |
| CN105214503A (en) * | 2015-10-14 | 2016-01-06 | 江南大学 | The hydrophilic method of repair membrane after Chemical cleaning |
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| CN103626922A (en) * | 2013-11-29 | 2014-03-12 | 内蒙古科技大学 | Method for preparing modified polyvinylidene fluoride one-step grafted 3-sulfonic acid propyl methacrylate (SPMA) proton exchange membrane |
| CN105214503A (en) * | 2015-10-14 | 2016-01-06 | 江南大学 | The hydrophilic method of repair membrane after Chemical cleaning |
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Application publication date: 20130904 |