CN103861481A - Method for preparing polyvinylidene-fluoride porous membrane - Google Patents
Method for preparing polyvinylidene-fluoride porous membrane Download PDFInfo
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- CN103861481A CN103861481A CN201410132425.8A CN201410132425A CN103861481A CN 103861481 A CN103861481 A CN 103861481A CN 201410132425 A CN201410132425 A CN 201410132425A CN 103861481 A CN103861481 A CN 103861481A
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- polyvinylidene fluoride
- kynoar
- polyethylene glycol
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Abstract
The invention discloses a method for preparing a polyvinylidene-fluoride porous membrane. The method comprises the steps of: (1) firstly mixing polyvinylidene fluoride with polyethylene glycol adipate, enabling the mixture to be completely dissolved in a dimethylformamide DMF organic solvent, standing for volatilizing into a membrane under the temperature of 60 DEG C; (2) heating and melting a blend membrane on a heating stage, insulating for 10 minutes and eliminating the heat history; (3) rapidly cooling blend melt to 155DEG C at the rate of 50 DEG C/min, utilizing a polymethyl siloxane plate to rapidly apply shearing stress of 104-105Pa to the blend melt on the heating stage; (4) standing and culturing a blend membrane on the heating stage with the temperature being 155 DEG C; (5) soaking completely-crystallized blend membrane in chloroformic solution, soaking for 72 hours, etching the polyethylene glycol adipate component completely, at the moment, only remaining polyvinylidene fluoride crystal for the blend membrane component, drying in a baking oven and thus obtaining the polyvinylidene-fluoride porous membrane. The method disclosed by the invention has the advantages that the process is simple and easy, the cost is low, and the industrial production and application is easy; the pore flux is high and the hydrophilcity and the pollution resistance are improved.
Description
Technical field
The invention belongs to and prepare porous membrane technical field take Kynoar as main component, be specifically related to one and prepare polyvinylidene fluoride porous film method.
Background technology
Polyvinylidene fluoride resin has the characteristic of fluororesin and resins for universal use, it is except having good chemical resistance, heat-resisting quantity, weatherability, also have the property such as piezoelectricity, electric heating, Kynoar is widely used in a lot of fields accordingly.
Research in recent years, Kynoar is because of its good film forming and excellent film properties, and Kynoar is usually applied in membrane separation technique, especially has very important effect in the effect aspect water resource utilization and environmental protection.But in polyvinylidene fluoride film molecular structure, contain bond energy higher-C-F key, its membrane material surface making is with water without hydrogen bond action, this makes film easily adsorb organic solute and contaminated.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of this invention is to provide a kind of method of preparing polyvinylidene fluoride porous film.Have easy to operation, the raw material feature that is easy to suitability for industrialized production cheap and easy to get.To achieve these goals, the technical solution used in the present invention is: a kind of method of preparing polyvinylidene fluoride porous film, includes following steps:
1), first according to Kynoar: the mass percent of polyethylene glycol adipate=30～70:30～70 is mixed, and it is dissolved in nitrogen dimethylformamide DMF organic solvent completely, utilize and be rotated into embrane method standing volatilization film forming at 60 ℃;
2), by blend film heating and melting on the hot platform of 195 ℃～205 ℃, insulation 10min, eliminates thermal history;
3) blend melt is cooled to rapidly to 155 ℃ with the speed of 50 ℃/min, on 155 ℃ of hot platforms, utilize polymethyl siloxane plate fast blend melt to be applied to 10
4～10
5the shear stress of Pa;
4) blend thin films leaves standstill and cultivates 12h～72h on the hot platform of 155 ℃;
5) by crystallization completely blend thin films be immersed in chloroformic solution, soak 72h, make the etching of polyethylene glycol adipate composition complete, now blend thin films composition only remains Kynoar crystal, in 60 ℃ of baking ovens, dry 8h, obtains polyvinylidene fluoride porous film.
the invention has the beneficial effects as follows:
The present invention is intended to prepare a kind of polyvinylidene fluoride porous film, makes it have good transparent performance, has good hydrophilicity, and antifouling property in the life-span of increase perforated membrane, makes its pore diameter reach 0.8～8 μ m.Can filter the particulate detecting in solvent, reagent, lubricating oil and solution, filter the following particle of 1.0 μ m.
Because the present invention has adopted Kynoar to have like this stability to have the organic resin of certain thermoelectricity capability simultaneously, by finding a kind of polyethylene glycol adipate compatible with Kynoar, interact by the CH2 in C=O and Kynoar in polyethylene glycol adipate, change the crystallinity of Kynoar, obtained hydrophilic Kynoar porous film material after then removing a kind of component by etched mode.Make the membrane material hole density that makes larger, porosity is high, and water flux is large, has improved the hydrophily of polyvinylidene fluoride material from microstructure.
Become so improve the pore diameter of polyvinylidene fluoride film the primary approach of preparing perforated membrane, for the anti-soil antibiotic property of PVDF membrane material provides solution.
Micropore filtering film is that a lot of micropores and the more uniform polymeric membrane of pore-size distribution are contained in a kind of inside, and its aperture generally, between 0.03～65 μ m, can separate proton or particle by pore size.Hydrophilic micropore filtering film is for fluid separation applications, and hydrophobic micropore filtering film is for gas solid separation.The pore size difference of micropore filtering film, its purposes is also different.
The present invention has adopted organic material to replace traditional inorganic material, simultaneously easy to operation, raw material is cheap and easy to get, the present invention also aims to provide a kind of technique simple, can strengthen hydrophily, the resistance tocrocking of film, extend the preparation method of the hydrophilicity kynoar perforated membrane in the life-span of film.
Accompanying drawing explanation
Fig. 1 is the design sketch of the embodiment of polyvinylidene fluoride film hydrophilically of the present invention, and wherein Fig. 1 (a) is Kynoar/polyethylene glycol adipate=70/30 electron-microscope scanning figure of the present invention; Fig. 1 (b) is Kynoar/polyethylene glycol adipate=30/7 electron-microscope scanning figure of the present invention.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
embodiment mono-
A method of preparing polyvinylidene fluoride porous film, includes following steps:
1), first according to Kynoar: the mass percent of polyethylene glycol adipate=70:30 is mixed, and it is dissolved in nitrogen dimethylformamide DMF organic solvent completely, utilize and be rotated into embrane method standing volatilization film forming at 60 ℃;
2), by blend film heating and melting on the hot platform of 195 ℃, insulation 10min, eliminates thermal history;
3) by step 2) blend melt prepared cools to rapidly 155 ℃ with the speed of 50 ℃/min, on 155 ℃ of hot platforms, utilizes polymethyl siloxane plate fast blend melt to be applied to 10
4shear stress;
4) blend thin films leaves standstill and cultivates 12h on the hot platform of 155 ℃;
5) by crystallization completely blend thin films be immersed in chloroformic solution, soak 72h, make the etching of polyethylene glycol adipate composition complete, now blend thin films composition only remains Kynoar crystal, in 60 ℃ of baking ovens, dry 8h, obtains polyvinylidene fluoride porous film.
The average aperture diameter of this polyvinylidene fluoride porous film is at 2.3 μ m.The contact angle of porous film surface water is 71.4 °.
embodiment bis-
A method of preparing polyvinylidene fluoride porous film, includes following steps:
, it is characterized in that, include following steps:
1), first according to Kynoar: the mass percent of polyethylene glycol adipate=50:50 is mixed, and it is dissolved in nitrogen dimethylformamide DMF organic solvent completely, utilize and be rotated into embrane method standing volatilization film forming at 60 ℃;
2), by blend film heating and melting on the hot platform at 205 ℃, insulation 10min, eliminates thermal history;
3) blend melt is cooled to rapidly to 155 ℃ with the speed of 50 ℃/min, on 155 ℃ of hot platforms, utilize polymethyl siloxane plate fast blend melt to be applied to 10
5the shear stress of Pa;
4) blend thin films leaves standstill and cultivates 72h on the hot platform of 155 ℃;
5) by crystallization completely blend thin films be immersed in chloroformic solution, soak 72h, make the etching of polyethylene glycol adipate composition complete, now blend thin films composition only remains Kynoar crystal, in 60 ℃ of baking ovens, dry 8h, obtains polyvinylidene fluoride porous film.
The average aperture diameter of this polyvinylidene fluoride porous film is at 3.4 μ m.The contact angle of porous film surface water is 68.6 °.
embodiment tri-
A method of preparing polyvinylidene fluoride porous film, includes following steps:
1), first according to Kynoar: the mass percent of polyethylene glycol adipate=30:70 is mixed, and it is dissolved in nitrogen dimethylformamide DMF organic solvent completely, utilize and be rotated into embrane method standing volatilization film forming at 60 ℃;
2), by blend film heating and melting on the hot platform at 200 ℃, insulation 10min, eliminates thermal history;
3) blend melt is cooled to rapidly to 155 ℃ with the speed of 50 ℃/min, on 155 ℃ of hot platforms, utilize polymethyl siloxane plate fast blend melt to be applied to 10
5the shear stress of Pa;
4) blend thin films leaves standstill and cultivates 60h on the hot platform of 155 ℃;
5) by crystallization completely blend thin films be immersed in chloroformic solution, soak 72h, make the etching of polyethylene glycol adipate composition complete, now blend thin films composition only remains Kynoar crystal, in 60 ℃ of baking ovens, dry 8h, obtains polyvinylidene fluoride porous film.
The average aperture diameter of this polyvinylidene fluoride porous film is at 5.8 μ m.The contact angle of porous film surface water is 53.4 °.
Judge pore diameter and the close hydrophobic property of polyvinylidene fluoride porous film by the contact angle of ESEM and test membrane surface water, can be found out by case study on implementation.Kynoar: ethylene glycol adipate=70:30, Kynoar: ethylene glycol adipate=50:50, Kynoar: ethylene glycol adipate=30:70, along with the increase of ethylene glycol adipate mass fraction, the aperture diameter of polyvinylidene fluoride porous film is also by 2.3 μ m, be increased to 3.4 μ m and 5.8 μ m, illustrate that aperture diameter has increased, be conducive to passing through of solia particle, film surface water contact angle has also been increased by 71.4 ° of hydrophilies of being down to 68.6 ° and 53.4 ° explanation polyvinylidene fluoride porous films, thereby improve the antifouling property of perforated membrane, increase the recycling rate of waterused of film, economic environmental protection.Therefore the perforated membrane that this method makes has very large economic worth.
Claims (4)
1. prepare a polyvinylidene fluoride porous film method, it is characterized in that, include following steps:
1), first according to Kynoar: the mass percent of polyethylene glycol adipate=30～70:30～70 is mixed, and it is dissolved in nitrogen dimethylformamide DMF organic solvent completely, utilize and be rotated into embrane method standing volatilization film forming at 60 ℃;
2), by blend film heating and melting on the hot platform of 195 ℃～205 ℃, insulation 10min, eliminates thermal history;
3) by step 2) blend melt prepared cools to rapidly 155 ℃ with the speed of 50 ℃/min, on 155 ℃ of hot platforms, utilizes polymethyl siloxane plate fast blend melt to be applied to 10
4～10
5the shear stress of Pa;
4) blend thin films leaves standstill and cultivates 12h～72h on the hot platform of 155 ℃;
5) by crystallization completely blend thin films be immersed in chloroformic solution, soak 72h, make the etching of polyethylene glycol adipate composition complete, now blend thin films composition only remains Kynoar crystal, in 60 ℃ of baking ovens, dry 8h, obtains polyvinylidene fluoride porous film.
2. a kind of method of preparing polyvinylidene fluoride porous film according to claim 1, is characterized in that, includes following steps:
1), first according to Kynoar: the mass percent of polyethylene glycol adipate=70:30 is mixed, and it is dissolved in nitrogen dimethylformamide DMF organic solvent completely, utilize and be rotated into embrane method standing volatilization film forming at 60 ℃;
2), by blend film heating and melting on the hot platform of 195 ℃, insulation 10min, eliminates thermal history;
3) by step 2) blend melt prepared cools to rapidly 155 ℃ with the speed of 50 ℃/min, on 155 ℃ of hot platforms, utilizes polymethyl siloxane plate fast blend melt to be applied to 10
4shear stress;
4) blend thin films leaves standstill and cultivates 12h on the hot platform of 155 ℃;
5) by crystallization completely blend thin films be immersed in chloroformic solution, soak 72h, make the etching of polyethylene glycol adipate composition complete, now blend thin films composition only remains Kynoar crystal, in 60 ℃ of baking ovens, dry 8h, obtains polyvinylidene fluoride porous film.
3. a kind of method of preparing polyvinylidene fluoride porous film according to claim 1, is characterized in that, includes following steps:
1), first according to Kynoar: the mass percent of polyethylene glycol adipate=50:50 is mixed, and it is dissolved in nitrogen dimethylformamide DMF organic solvent completely, utilize and be rotated into embrane method standing volatilization film forming at 60 ℃;
2), by blend film heating and melting on the hot platform at 205 ℃, insulation 10min, eliminates thermal history;
3) blend melt is cooled to rapidly to 155 ℃ with the speed of 50 ℃/min, on 155 ℃ of hot platforms, utilize polymethyl siloxane plate fast blend melt to be applied to 10
5the shear stress of Pa;
4) blend thin films leaves standstill and cultivates 72h on the hot platform of 155 ℃;
5) by crystallization completely blend thin films be immersed in chloroformic solution, soak 72h, make the etching of polyethylene glycol adipate composition complete, now blend thin films composition only remains Kynoar crystal, in 60 ℃ of baking ovens, dry 8h, obtains polyvinylidene fluoride porous film.
4. a kind of method of preparing polyvinylidene fluoride porous film according to claim 1, is characterized in that, includes following steps:
1), first according to Kynoar: the mass percent of polyethylene glycol adipate=30:70 is mixed, and it is dissolved in nitrogen dimethylformamide DMF organic solvent completely, utilize and be rotated into embrane method standing volatilization film forming at 60 ℃;
2), by blend film heating and melting on the hot platform at 200 ℃, insulation 10min, eliminates thermal history;
3) blend melt is cooled to rapidly to 155 ℃ with the speed of 50 ℃/min, on 155 ℃ of hot platforms, utilize polymethyl siloxane plate fast blend melt to be applied to 10
5the shear stress of Pa;
4) blend thin films leaves standstill and cultivates 60h on the hot platform of 155 ℃;
5) by crystallization completely blend thin films be immersed in chloroformic solution, soak 72h, make the etching of polyethylene glycol adipate composition complete, now blend thin films composition only remains Kynoar crystal, in 60 ℃ of baking ovens, dry 8h, obtains polyvinylidene fluoride porous film.
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| CN201410132425.8A CN103861481B (en) | 2014-04-03 | 2014-04-03 | A kind of method preparing polyvinylidene fluoride porous film |
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| CN103861481B CN103861481B (en) | 2015-11-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092934A (en) * | 2019-06-06 | 2019-08-06 | 北京化工大学 | Promote the method for Kynoar crystal transfer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269302A (en) * | 2008-05-06 | 2008-09-24 | 南京奥特高科技有限公司 | Non-crystallization permanent hydrophilic PVDF membrane material and preparation method thereof |
| CN102198371A (en) * | 2011-05-24 | 2011-09-28 | 东华大学 | Blend membrane of polyvinyl butyral (PVB) and polyvinylidene fluoride (PVDF) and preparation method thereof |
| WO2013073828A1 (en) * | 2011-11-16 | 2013-05-23 | 엘지전자 주식회사 | Hydrophilic polyvinylidene fluoride-based hollow-fiber separation membrane, and method for manufacturing same |
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2014
- 2014-04-03 CN CN201410132425.8A patent/CN103861481B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269302A (en) * | 2008-05-06 | 2008-09-24 | 南京奥特高科技有限公司 | Non-crystallization permanent hydrophilic PVDF membrane material and preparation method thereof |
| CN102198371A (en) * | 2011-05-24 | 2011-09-28 | 东华大学 | Blend membrane of polyvinyl butyral (PVB) and polyvinylidene fluoride (PVDF) and preparation method thereof |
| WO2013073828A1 (en) * | 2011-11-16 | 2013-05-23 | 엘지전자 주식회사 | Hydrophilic polyvinylidene fluoride-based hollow-fiber separation membrane, and method for manufacturing same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092934A (en) * | 2019-06-06 | 2019-08-06 | 北京化工大学 | Promote the method for Kynoar crystal transfer |
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Granted publication date: 20151104 |