CN104043351A - Grafting modification method for anti-pollution polyvinylidene fluoride flat plate ultra-filtration membrane - Google Patents
Grafting modification method for anti-pollution polyvinylidene fluoride flat plate ultra-filtration membrane Download PDFInfo
- Publication number
- CN104043351A CN104043351A CN201410267427.8A CN201410267427A CN104043351A CN 104043351 A CN104043351 A CN 104043351A CN 201410267427 A CN201410267427 A CN 201410267427A CN 104043351 A CN104043351 A CN 104043351A
- Authority
- CN
- China
- Prior art keywords
- pollution
- membrane
- ultrafiltration membrane
- graft
- modification method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a grafting modification method for an anti-pollution polyvinylidene fluoride flat plate ultra-filtration membrane. The method comprises the following specific steps: (1) dissolving dried polyvinylidene fluoride into a solvent; adding a pore forming agent; agitating by a magnetic force, and standing and de-foaming; (2) preparing an ultra-filtration membrane by using an immersion phase inversion method; after scraping the membrane, immersing into a coagulating bath to form a membrane; (3) immersing the membrane in water and replacing the water by distilled water until the solvent and the pore forming agent are removed; and (4) preparing a monomer and initiator mixed water solution; spraying the mixed solution on the surface of the membrane by using a spraying method; radiating by ultraviolet light; and washing the modified membrane by the distilled water to remove un-reacted monomer and initiator. The method is used for carrying out grafting modification on the flat plate ultra-filtration membrane; the concentrations of the monomer and the initiator are easy to control and the operation is simple and feasible. An experiment shows that after ultraviolet grafting, the flux of pure water slightly decreases and the contact angle of the water on the surface of the membrane is greatly reduced; the mechanical property of the membrane is certainly improved and the anti-pollution capability is greatly enhanced.
Description
Technical field
The present invention relates to flat plate ultrafiltration membrane modification technology field, relate in particular to a kind of graft-modification method of anti-pollution vinylidene difluoride planar ultrafiltration membrane.
Background technology
Kynoar is heat-resisting because of it, and resistance to chemical attack, resistance to ultraviolet and high-energy radiation and the advantage such as cheap, be widely used in the preparation of milipore filter.But the hydrophily of itself is poor, in application, easily cause film to pollute.
The absorption of protein is the one of the main reasons that film pollutes.In fenestra, adsorbed protein, can change effective aperture and the pore-size distribution of film, thereby affected flux and the cutoff performance of film, film surface, because of the gel layer that pollution forms, has increased film to the micromolecular resistance that sees through, can the serious effective flux that reduces film.Therefore need improve the hydrophily on film surface, to reduce its absorption to protein molecule, improve the antifouling property of film.
At present, the film surface hydrophilic modification method of having reported mainly comprises chemical modification, ultra-violet radiation grafting, gamma-rays grafting and Low Temperature Plasma Treating etc.Wherein, ultra-violet radiation Graft Method owing to being swift in response, cost is low, equipment is simple and be easy to industry amplifies and receive much concern.In addition, graft reaction mainly occurs in film surface, can significantly not affect mechanical strength and the separating property of film.In document, generally adopt film immersed to the method in initator and grafted monomers, after carry out ultraviolet irradiation processing.But the concentration of solution is wayward like this, causes the loss of monomer and initator, and surrounding environment has been caused to pollution to a certain degree.
Summary of the invention
The invention provides a kind of graft-modification method of anti-pollution vinylidene difluoride planar ultrafiltration membrane.
Anti-pollution vinylidene difluoride planar ultrafiltration membrane of the present invention is: take Kynoar as filmogen, adopt phase inversion to prepare vinylidene difluoride planar ultrafiltration membrane, take ceric sulfate as initator, maleic anhydride is grafted monomers, adopts spray process that the two mixed aqueous solution is grafted on to polyvinylidene fluoride (PVDF) ultrafiltration membrane surface.
The technical scheme that the present invention takes is:
The concrete steps of the graft-modification method of anti-pollution vinylidene difluoride planar ultrafiltration membrane of the present invention are as follows:
(1) after Kynoar is dried, be dissolved in solvent, and add pore-foaming agent, stir, obtain the polymer solution of clear, then put into baking oven, standing and defoaming;
(2) after the even deaeration of solution, by knifing machine striking film forming on nonwoven; At air evaporation 5-20s, evaporating temperature 15-30 ℃, envionmental humidity 30-50%, gel forming in the coagulating bath that 20 ℃ of distilled water of rear rapid immersion form;
(3) film preparing soaks 24-48h in distilled water, during every 8 hours, change first water, remove solvent and additive wherein;
(4) preparation monomer, initator mixed aqueous solution, adopt spray process that mixed solution is sprayed to film surface, with 2000W ultraviolet light irradiation 5 minutes, distilled water cleaned 3 times for the diaphragm of modification, to remove unreacted monomer and initator, can make polyvinylidene fluoride (PVDF) ultrafiltration membrane of the present invention.
In step (1), Kynoar furnace drying method is: more than Kynoar is dried to 24h at 60 ℃.
In step (1), solvent is DMA, and pore-foaming agent is the mixture of PVP K30 and cetomacrogol 1000, and wherein the weight ratio of PVP K30 and cetomacrogol 1000 is 1:1.
In step (1), polymer solution percentage by weight is composed as follows: Kynoar 10-30%, pore-foaming agent 1-10%, solvent 60-85%.Preferred polymers solution weight percentage is composed as follows: Kynoar 17%, pore-foaming agent 5%, solvent 78%.
In step (1), preferably put into 60 ℃ of baking ovens, standing and defoaming.
In step (4), described monomer is that maleic anhydride, described initator are ceric sulfates.
In step (4), the concentration of monomer is 0.01-0.20mol/L, and initiator concentration is 0.07mol/L.
Good effect of the present invention is as follows:
1) adopt method of the present invention to carry out graft modification to flat plate ultrafiltration membrane, monomer and initiator concentration are easy to control, and operation is simple.
2) experiment is found, after uv photo initiated grafting, pure water flux slightly declines, and water reduces greatly at the contact angle on film surface.
3), after uv photo initiated grafting, the mechanical property of polyvinylidene fluoride (PVDF) ultrafiltration membrane has some improvement.
4) diaphragm before and after graft modification is carried out to antipollution experiment, the polyvinylidene fluoride (PVDF) ultrafiltration membrane after the results show modification of the present invention has the following advantages:
After grafting, the flux decline degree of milipore filter reduces greatly, illustrates that the contamination resistance of film improves greatly.
The specific embodiment
The following examples are to describe in further detail of the present invention.
Embodiment 1
(1) after Kynoar is dried, be dissolved in solvent, and add pore-foaming agent, stir, obtain the polymer solution of clear, then put into baking oven, standing and defoaming;
(2) after the even deaeration of solution, by knifing machine striking film forming on nonwoven; At air evaporation 5s, 30 ℃ of evaporating temperatures, envionmental humidity 30%, gel forming in the coagulating bath that 20 ℃ of distilled water of rear rapid immersion form;
(3) film preparing soaks 24h in distilled water, during it was changed to first water every 8 hours, remove solvent and additive wherein;
(4) preparation monomer, initator mixed aqueous solution, adopt spray process that mixed solution is sprayed to film surface, with 2000W ultraviolet light irradiation 5 minutes, distilled water cleaned 3 times for the diaphragm of modification, to remove unreacted monomer and initator, can make polyvinylidene fluoride (PVDF) ultrafiltration membrane of the present invention.
In step (1), Kynoar furnace drying method is: more than Kynoar is dried to 24h at 60 ℃.
In step (1), solvent is DMA, and pore-foaming agent is the mixture of PVP K30 and cetomacrogol 1000, and wherein the weight ratio of PVP K30 and cetomacrogol 1000 is 1:1.
In step (1), polymer solution percentage by weight is composed as follows: Kynoar 10%, pore-foaming agent 5%, solvent 85%.
In step (1), put in advance 60 ℃ of baking ovens, standing and defoaming.
In step (4), described monomer is that maleic anhydride, described initator are ceric sulfates.
In step (4), the concentration of monomer is 0.05mol/L, and initiator concentration is 0.07mol/L.
Embodiment 2
(1) after Kynoar is dried, be dissolved in solvent, and add pore-foaming agent, stir, obtain the polymer solution of clear, then put into baking oven, standing and defoaming;
(2) after the even deaeration of solution, by knifing machine striking film forming on nonwoven; At air evaporation 20s, 15 ℃ of evaporating temperatures, envionmental humidity 50%, gel forming in the coagulating bath that 20 ℃ of distilled water of rear rapid immersion form;
(3) film preparing soaks 48h in distilled water, during every 8 hours, change first water, remove solvent and additive wherein;
(4) preparation monomer, initator mixed aqueous solution, adopt spray process that mixed solution is sprayed to film surface, with 2000W ultraviolet light irradiation 5 minutes, distilled water cleaned 3 times for the diaphragm of modification, to remove unreacted monomer and initator, can make polyvinylidene fluoride (PVDF) ultrafiltration membrane of the present invention.
In step (1), Kynoar furnace drying method is: more than Kynoar is dried to 24h at 60 ℃.
In step (1), solvent is DMA, and pore-foaming agent is the mixture of PVP K30 and cetomacrogol 1000, and wherein the weight ratio of PVP K30 and cetomacrogol 1000 is 1:1.
In step (1), polymer solution percentage by weight is composed as follows: Kynoar 30%, pore-foaming agent 1%, solvent 69%.
In step (1), put in advance 60 ℃ of baking ovens, standing and defoaming.
In step (4), described monomer is that maleic anhydride, described initator are ceric sulfates.
In step (4), the concentration of monomer is 0.10mol/L, and initiator concentration is 0.07mol/L.
Embodiment 3
(1) after Kynoar is dried, be dissolved in solvent, and add pore-foaming agent, stir, obtain the polymer solution of clear, then put into baking oven, standing and defoaming;
(2) after the even deaeration of solution, by knifing machine striking film forming on nonwoven; At air evaporation 15s, 25 ℃ of evaporating temperatures, envionmental humidity 40%, gel forming in the coagulating bath that 20 ℃ of distilled water of rear rapid immersion form;
(3) film preparing soaks 36h in distilled water, during every 8 hours, change first water, remove solvent and additive wherein;
(4) preparation monomer, initator mixed aqueous solution, adopt spray process that mixed solution is sprayed to film surface, with 2000W ultraviolet light irradiation 5 minutes, distilled water cleaned 3 times for the diaphragm of modification, to remove unreacted monomer and initator, can make vinylidene milipore filter of the present invention.
In step (1), Kynoar furnace drying method is: more than Kynoar is dried to 24h at 60 ℃.
In step (1), solvent is DMA, and pore-foaming agent is the mixture of PVP K30 and cetomacrogol 1000, and wherein the weight ratio of PVP K30 and cetomacrogol 1000 is 1:1.
In step (1), polymer solution percentage by weight is composed as follows: Kynoar 17%, pore-foaming agent 5%, solvent 78%.
In step (1), put in advance 60 ℃ of baking ovens, standing and defoaming.
In step (4), described monomer is that maleic anhydride, described initator are ceric sulfates.
In step (4), the concentration of monomer is 0.15mol/L, and the concentration of initator is 0.07mol/L.
The performance of polyvinylidene fluoride (PVDF) ultrafiltration membrane prepared by the present invention:
Polyvinylidene fluoride (PVDF) ultrafiltration membrane prepared by the present invention detects as follows:
Experimental technique is as follows:
1. adopt contact angle tester to measure water at the contact angle on polyvinylidene fluoride (PVDF) ultrafiltration membrane surface.
2. adopt self-control ultrafiltration cup to measure the pure water flux of polyvinylidene fluoride (PVDF) ultrafiltration membrane.
3. adopt mechanical test machine to measure the tensile property of polyvinylidene fluoride (PVDF) ultrafiltration membrane.
Experimental result:
Experiment discovery, after uv photo initiated grafting, the contact angle of polyvinylidene fluoride (PVDF) ultrafiltration membrane surface water reduces greatly.
The pure water flux of film slightly declines, and after uv photo initiated grafting modification, the mechanical property of film has some improvement.
Antipollution experiment:
Adopt homemade ultrafiltration cup to carry out antipollution experiment, first precompressed 30min under 0.15MPa then measures milipore filter and filters 100ml running water time t used under 0.1MPa
1, the milipore filter 20min after ultrasonic cleaning is polluted, then repeats above precompressed process, redeterminates milipore filter and filter 100ml running water time t used under 0.1MPa
2, the D=(t for attenuation degree of film
2-t
1)/t
2* 100% calculates.
Antipollution experimental result:
Take embodiment 1 as example, and the milipore filter maximum stress making is 3.87N/mm
2, fracture strength is 3.86N/mm
2, flux decline degree is 59.8%, after uv photo initiated grafting modification, the maximum stress of film is 3.98N/mm
2, fracture strength is 3.97N/mm
2, flux decline degree is 4.9%.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (8)
1. a graft-modification method for anti-pollution vinylidene difluoride planar ultrafiltration membrane, is characterized in that: the concrete steps of described method are as follows:
(1) after Kynoar is dried, be dissolved in solvent, and add pore-foaming agent, stir, obtain the polymer solution of clear, then put into baking oven, standing and defoaming;
(2) after the even deaeration of solution, by knifing machine striking film forming on nonwoven; At air evaporation 5-20s, evaporating temperature 15-30 ℃, envionmental humidity 30-50%, gel forming in the coagulating bath that 20 ℃ of distilled water of rear rapid immersion form;
(3) film preparing soaks 24-48h in distilled water, during every 8 hours, change first water, remove solvent and additive wherein;
(4) preparation monomer, initator mixed aqueous solution, adopt spray process that mixed solution is sprayed to film surface, with 2000W ultraviolet light irradiation 5 minutes, the diaphragm of modification cleans 3 times with distilled water, to remove unreacted monomer and initator, can make vinylidene difluoride planar ultrafiltration membrane of the present invention.
2. the graft-modification method of anti-pollution vinylidene difluoride planar ultrafiltration membrane as claimed in claim 1, is characterized in that: in step (1), Kynoar furnace drying method is: more than Kynoar is dried to 24h at 60 ℃.
3. the graft-modification method of anti-pollution vinylidene difluoride planar ultrafiltration membrane as claimed in claim 1, it is characterized in that: in step (1), solvent is N, N-dimethylacetylamide, pore-foaming agent is the mixture of PVP K30 and cetomacrogol 1000, and wherein the weight ratio of PVP K30 and cetomacrogol 1000 is 1:1.
4. the graft-modification method of anti-pollution vinylidene difluoride planar ultrafiltration membrane as claimed in claim 1, it is characterized in that: in step (1), polymer solution percentage by weight is composed as follows: Kynoar 10-30%, pore-foaming agent 1-10%, solvent 60-85%.
5. the graft-modification method of anti-pollution vinylidene difluoride planar ultrafiltration membrane as claimed in claim 1, is characterized in that: in step (1), polymer solution percentage by weight is composed as follows: Kynoar 17%, pore-foaming agent 5%, solvent 78%.
6. the graft-modification method of anti-pollution vinylidene difluoride planar ultrafiltration membrane as claimed in claim 1, is characterized in that: in step (1), put into 60 ℃ of baking ovens, standing and defoaming.
7. the graft-modification method of anti-pollution vinylidene difluoride planar ultrafiltration membrane as claimed in claim 1, is characterized in that: in step (4), described monomer is that maleic anhydride, described initator are ceric sulfates.
8. the graft-modification method of anti-pollution vinylidene difluoride planar ultrafiltration membrane as claimed in claim 1, is characterized in that: in step (4), the concentration of monomer is 0.01-0.20mol/L, and initiator concentration is 0.07mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410267427.8A CN104043351A (en) | 2014-06-16 | 2014-06-16 | Grafting modification method for anti-pollution polyvinylidene fluoride flat plate ultra-filtration membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410267427.8A CN104043351A (en) | 2014-06-16 | 2014-06-16 | Grafting modification method for anti-pollution polyvinylidene fluoride flat plate ultra-filtration membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104043351A true CN104043351A (en) | 2014-09-17 |
Family
ID=51497043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410267427.8A Pending CN104043351A (en) | 2014-06-16 | 2014-06-16 | Grafting modification method for anti-pollution polyvinylidene fluoride flat plate ultra-filtration membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104043351A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504319A (en) * | 2015-12-23 | 2016-04-20 | 厦门理工学院 | Anthraquinone functionalized polyvinylidene fluoride membrane as well as preparation method and application thereof |
| CN111545079A (en) * | 2020-05-15 | 2020-08-18 | 江苏拓邦环保科技有限公司 | Novel and improved preparation method of PVDF (polyvinylidene fluoride) flat ultrafiltration membrane |
| CN116870701A (en) * | 2023-09-08 | 2023-10-13 | 杭州尚善若水环保科技有限公司 | Anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5531900A (en) * | 1994-07-07 | 1996-07-02 | University Of Arizona | Modification of polyvinylidene fluoride membrane and method of filtering |
| WO2004009201A2 (en) * | 2002-07-24 | 2004-01-29 | Cuno, Inc. | Polymeric surface treatment of filter media |
| KR20110131794A (en) * | 2010-05-31 | 2011-12-07 | 경상대학교산학협력단 | Method for preparing of high permeable hollow fiber membrane supports |
| CN102553464A (en) * | 2011-12-30 | 2012-07-11 | 江苏大孚膜科技有限公司 | Preparation method of modified polyvinylidene fluoride ultrafiltration membrane |
| CN103357275A (en) * | 2013-06-26 | 2013-10-23 | 三达膜科技（厦门）有限公司 | Ultrafiltration membrane after-treatment modification method |
| CN103623716A (en) * | 2013-12-02 | 2014-03-12 | 北京碧水源膜科技有限公司 | Method for establishing PVDF micro-filtration membrane super-hydrophilic layer |
-
2014
- 2014-06-16 CN CN201410267427.8A patent/CN104043351A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5531900A (en) * | 1994-07-07 | 1996-07-02 | University Of Arizona | Modification of polyvinylidene fluoride membrane and method of filtering |
| WO2004009201A2 (en) * | 2002-07-24 | 2004-01-29 | Cuno, Inc. | Polymeric surface treatment of filter media |
| KR20110131794A (en) * | 2010-05-31 | 2011-12-07 | 경상대학교산학협력단 | Method for preparing of high permeable hollow fiber membrane supports |
| CN102553464A (en) * | 2011-12-30 | 2012-07-11 | 江苏大孚膜科技有限公司 | Preparation method of modified polyvinylidene fluoride ultrafiltration membrane |
| CN103357275A (en) * | 2013-06-26 | 2013-10-23 | 三达膜科技（厦门）有限公司 | Ultrafiltration membrane after-treatment modification method |
| CN103623716A (en) * | 2013-12-02 | 2014-03-12 | 北京碧水源膜科技有限公司 | Method for establishing PVDF micro-filtration membrane super-hydrophilic layer |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504319A (en) * | 2015-12-23 | 2016-04-20 | 厦门理工学院 | Anthraquinone functionalized polyvinylidene fluoride membrane as well as preparation method and application thereof |
| WO2017107658A1 (en) * | 2015-12-23 | 2017-06-29 | 厦门理工学院 | Polyvinylidene fluoride film having functional anthraquinone, method of preparing same, and application thereof |
| CN105504319B (en) * | 2015-12-23 | 2018-06-12 | 厦门理工学院 | A kind of polyvinylidene fluoride film of anthraquinone functionalization and preparation method and application |
| CN111545079A (en) * | 2020-05-15 | 2020-08-18 | 江苏拓邦环保科技有限公司 | Novel and improved preparation method of PVDF (polyvinylidene fluoride) flat ultrafiltration membrane |
| CN116870701A (en) * | 2023-09-08 | 2023-10-13 | 杭州尚善若水环保科技有限公司 | Anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage |
| CN116870701B (en) * | 2023-09-08 | 2023-11-21 | 杭州尚善若水环保科技有限公司 | Anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100345616C (en) | Polymer microporous modification by corona induced grafting technology | |
| CN100337727C (en) | Microporous polymer film containing cross-linked super branched molecule and its prepn | |
| CN102512971B (en) | Method for preparing composite flat ultrafiltration membrane | |
| CN101439266A (en) | Surface modification method of polymer microporous film | |
| CN102580574B (en) | Antipollution self-cleaning polyvinylidene fluoride membrane and method for producing same | |
| CN104548961A (en) | Preparation method for hydrophilic anti-fouling polyvinylidene fluoride membrane | |
| CN104043351A (en) | Grafting modification method for anti-pollution polyvinylidene fluoride flat plate ultra-filtration membrane | |
| KR20160022619A (en) | A preparation method of hydrophilic membrane and a hydrophilic membrane prepared by the same | |
| CN108097072A (en) | A kind of hydrophilic modifying CPVA-PVDF ultrafiltration membranes and preparation method thereof | |
| CN102728241A (en) | Anti-pollution separation membrane and preparation method | |
| CN103861465B (en) | A kind of hydrophobic separation membrane material surface surpasses the method for hydrophilic modifying | |
| CN107376673A (en) | One kind is loaded with TiO2PES milipore filters of nanotube and its preparation method and application | |
| CN103831027A (en) | Method for improving pollution resistance of PVDF (polyvinylidene fluoride) porous membrane based on plasmas technology | |
| CN103230747B (en) | Preparation method of composite film for water treatment | |
| CN105251377A (en) | Preparation method for polyvinylidene fluoride microfiltration membrane | |
| CN104150787B (en) | A kind of Induced by Dopamine sol-gal process prepares the method for modifying of high hydrophiling coating | |
| CN106474941A (en) | A kind of modified method of Pvdf Microporous Hollow Fiber Membrane surface hydrophobicity | |
| Mu et al. | Hydrophilic modification of polyethersulfone porous membranes via a thermal-induced surface crosslinking approach | |
| CN105833732B (en) | The modified seperation film and preparation method thereof of hydrophilic anti-pollution gel coat | |
| CN110975649A (en) | Modified polyvinylidene fluoride ultrafiltration membrane and preparation method thereof | |
| CN106076131A (en) | Effective Anti pollutes polymer separation film and preparation method thereof | |
| CN102643449A (en) | Method for preparing polymer porous membrane without solvent | |
| CN108043233B (en) | Oxidation-resistant polyamide reverse osmosis membrane and preparation method and application thereof | |
| CN103611430A (en) | Production method for high-ion selectivity hollow fibrous nanofiltration membrane | |
| CN104607071A (en) | Polyvinylidene fluoride hydrophilic membrane preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140917 |
|
| RJ01 | Rejection of invention patent application after publication |