CN101703897A - Preparation method of polyvinylidene fluoride (PVDF) ultrafiltration membrane with improved permeability - Google Patents
Preparation method of polyvinylidene fluoride (PVDF) ultrafiltration membrane with improved permeability Download PDFInfo
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- CN101703897A CN101703897A CN200910272756A CN200910272756A CN101703897A CN 101703897 A CN101703897 A CN 101703897A CN 200910272756 A CN200910272756 A CN 200910272756A CN 200910272756 A CN200910272756 A CN 200910272756A CN 101703897 A CN101703897 A CN 101703897A
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Abstract
The invention relates to a preparation method of a polyvinylidene fluoride (PVDF) ultrafiltration membrane with improved permeability. The preparation method adopts polyether sulphone (PES) as a blending material of the PVDF, and comprises the following steps: (1) adding the PES after dissolving the PVDF in N-N dimethyl acetamide; (2) adding and stirring polyvinyl pyrrolidone till the polyvinyl pyrrolidone is completely dissolved to form casting solution, standing for 24-48 hours, and defoaming; (3) forming the defoamed casting solution into a membrane by using an L-S phase inversion method; (4) putting the membrane after striking in coagulation bath for soaking for 48 hours; and (5) soaking the membrane taken out of the coagulation bath for 8-24 hours with 30% glycerin solution, and taking out and naturally drying the membrane to obtain the PVDF ultrafiltration membrane. The preparation method adopts the PES as the blending material of the PVDF so as to improve the shrinkage resistance of the blended membrane; and simultaneously, the PES is also very good hydrophilic material, so that the flow capacity of the membrane is greatly improved after the PES is blended with the PVDF, thus having extremely high industrial application value.
Description
Technical field
The present invention relates to and belongs to the membrane separation technique field, is specifically related to a kind of preparation method who improves the polyvinylidene fluoride (PVDF) ultrafiltration membrane of permeability.
Background technology
Kynoar (PVDF) is a kind of semicrystalline polymeric, and it has good dissolubility resistent, heat endurance and hydrolytic resistance, and the chemical attack of anti-multiple acid, alkali is good membrane material.The shortcoming of pvdf membrane has two: one, and PVDF has stronger hydrophobicity, causes film to pollute when handling proteinaceous liquid with it easily; The 2nd, pvdf membrane can significantly shrink in dry run, and voidage and average pore size are reduced.Pvdf membrane can improve its practicality by modification, and aspect the pvdf membrane modification, the focus that people pay close attention to is to improve the hydrophily of PVDF, but how to improve the anti-contracility no less important of pvdf membrane.
Summary of the invention
The objective of the invention is at the dry after-contraction of existing polyvinylidene fluoride (PVDF) ultrafiltration membrane greatlyyer, make the voidage of milipore filter and the problem that the aperture reduces significantly, propose the preparation method that a kind of method by blend is improved the polyvinylidene fluoride (PVDF) ultrafiltration membrane of permeability.
Technical solution of the present invention is: because blend is to improve the simple but effective method of polymer performance, the present invention adopts polyether sulfone (PES) to be the intermingling material of Kynoar, and the preparation method is as follows:
1. PVDF is dissolved in the solvent N-N dimethylacetylamide, treats to add PES again after the PVDF dissolving;
2. add the pore former PVP, evenly be stirred to dissolving formation casting solution fully, leave standstill deaeration in 24～48 hours;
3. the casting solution after the deaeration is used the L-S forming film with phase transformation method under 25 ℃～30 ℃ temperature, 60～80% relative humidity;
4. scrape the film that makes and put into coagulating bath immersion 48 hours;
5. the film that takes out from coagulating bath soaked 8～24 hours with 30% glycerite, took out air dry and made the PVDF milipore filter.
The proportioning of PVDF, N-N dimethylacetamide solvent, polyether sulfone, PVP pore former is as follows in above-mentioned preparation method:
PVDF 12％～20％
Solvent N-N dimethylacetylamide 78.5%～85.5%
Polyether sulfone 0.5%～1.5%
PVP pore former 2%～5%
The invention has the beneficial effects as follows: it is the intermingling material of PVDF that the inventive method has adopted polyether sulfone, be intended to improve the anti-contracility energy of blend film, polyether sulfone also is good water wetted material simultaneously, after the PVDF blend, the water-flowing amount of film significantly improves, have high industrial application value. aspect the shrinkage of anti-film, because the existence of phenyl ring in the big molecule of PES, make the barrier potential of rotation in the big molecule of PES higher, the strand compliance reduces, rigidity increases. under general baking temperature, PES is in glassy state, big molecule is rigidity, and its conformation can not freely change, because the effect of chain entanglement, PES is big, and molecule plays reinforcement effect as reinforcing bar in blend film, thereby can reduce the shrinkage factor of film effectively.
Description of drawings
Fig. 1 polyvinylidene fluoride (PVDF) ultrafiltration membrane top layer electron-microscope scanning figure
Fig. 2 polyvinylidene fluoride (PVDF) ultrafiltration membrane aperture electron-microscope scanning figure
The specific embodiment
Embodiment 1
(1) 12 gram PVDF are dissolved in treats in the 78.5 gram N-N dimethylacetylamides that it dissolves the back fully and adds 0.5 gram polyether sulfone.
(2) treat that polyether sulfone dissolves the back fully and adds 4 gram PVPs, evenly stirred 4～5 hours, form casting solution, leave standstill deaeration in 48 hours.
(3) casting solution after the deaeration is used the L-S forming film with phase transformation method under 25 ℃, 60% relative humidity.
(4) the knifing time of staying lacks as far as possible, and the film after scraping is put into rapidly and solidified bath water immersion 48 hours.
(5) soaked film takes out in the water.Put into 30% glycerite 24 hours, air dry after finishing.
Embodiment 2
(1) 12 gram PVDF is dissolved in the 78.5 gram N-N dimethylacetylamides, treat that it dissolves the back fully and adds 0.5 gram polyether sulfone.
(2) treat that polyether sulfone dissolves the back fully and adds 4 gram PVPs, evenly stirred 4～5 hours, form casting solution, leave standstill deaeration in 48 hours.
(3) casting solution after the deaeration is used the L-S forming film with phase transformation method under 25 ℃, 60% relative humidity.
(4) the knifing time of staying lacks as far as possible, and the film after scraping is put into the coagulating bath of being made up of 25%N-N dimethylacetylamide and 75% distilled water rapidly and soaked 5 minutes, puts into water after the taking-up and soaks 48 hours.
(5) soaked film takes out in the water, puts into 30% glycerite 24 hours, air dry after finishing.
Claims (2)
1. preparation method who improves the polyvinylidene fluoride (PVDF) ultrafiltration membrane of permeability, it is characterized in that adopting polyether sulfone is the intermingling material of Kynoar, the preparation process of milipore filter is as follows:
1. Kynoar is dissolved in the solvent N-N dimethylacetylamide, treats to add polyether sulfone again after the Kynoar dissolving;
2. add the pore former PVP, evenly be stirred to dissolving formation casting solution fully, leave standstill deaeration in 24～48 hours;
3. the casting solution after the deaeration is used the L-S forming film with phase transformation method under 25 ℃～30 ℃ temperature, 60～80% relative humidity;
4. scrape the film that makes and put into coagulating bath immersion 48 hours;
5. the film that takes out from coagulating bath soaked 8～24 hours with 30% glycerite, took out air dry and made polyvinylidene fluoride (PVDF) ultrafiltration membrane.
2. a kind of preparation method who improves the polyvinylidene fluoride (PVDF) ultrafiltration membrane of permeability as claimed in claim 1 is characterized in that the proportioning of Kynoar, N-N dimethylacetamide solvent, polyether sulfone, PVP is as follows:
Kynoar 12%～20%
N-N dimethylacetylamide 78.5%～85.5%
Polyether sulfone 0.5%～1.5%
PVP 2%～5%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910272756A CN101703897A (en) | 2009-11-13 | 2009-11-13 | Preparation method of polyvinylidene fluoride (PVDF) ultrafiltration membrane with improved permeability |
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| CN200910272756A CN101703897A (en) | 2009-11-13 | 2009-11-13 | Preparation method of polyvinylidene fluoride (PVDF) ultrafiltration membrane with improved permeability |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626593A (en) * | 2012-04-13 | 2012-08-08 | 清华大学 | Formula of acid and alkali-resistant and anti-pollution ultrafiltration membrane and preparation method thereof |
| CN103736403A (en) * | 2013-12-20 | 2014-04-23 | 苏州膜华材料科技有限公司 | Preparation method of polyvinylidene fluoride/phenolphthalein side group polyarylethersulfone alloy membrane |
| CN103917287A (en) * | 2011-10-04 | 2014-07-09 | Mn投资有限公司 | Abrasion-proof filtration membrane and method of producing said membrane |
| CN106964264A (en) * | 2017-04-27 | 2017-07-21 | 苏州捷尔沃科技有限公司 | Self-supporting with superhydrophobic breathable property and the pvdf membrane containing substrate |
| CN107591545A (en) * | 2016-07-07 | 2018-01-16 | 中国科学院大连化学物理研究所 | A kind of application of blended porous membrane in flow battery |
| US11667782B2 (en) | 2020-09-09 | 2023-06-06 | Industrial Technology Research Institute | Polyvinylidene fluoride film composition, and polyvinylidene fluoride isolation film |
-
2009
- 2009-11-13 CN CN200910272756A patent/CN101703897A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103917287A (en) * | 2011-10-04 | 2014-07-09 | Mn投资有限公司 | Abrasion-proof filtration membrane and method of producing said membrane |
| CN103917287B (en) * | 2011-10-04 | 2017-05-17 | 迈纳德膜技术有限公司 | Abrasion-proof filtration membrane and method of producing said membrane |
| CN102626593A (en) * | 2012-04-13 | 2012-08-08 | 清华大学 | Formula of acid and alkali-resistant and anti-pollution ultrafiltration membrane and preparation method thereof |
| CN102626593B (en) * | 2012-04-13 | 2015-05-06 | 清华大学 | Formula of acid and alkali-resistant and anti-pollution ultrafiltration membrane and preparation method thereof |
| CN103736403A (en) * | 2013-12-20 | 2014-04-23 | 苏州膜华材料科技有限公司 | Preparation method of polyvinylidene fluoride/phenolphthalein side group polyarylethersulfone alloy membrane |
| CN107591545A (en) * | 2016-07-07 | 2018-01-16 | 中国科学院大连化学物理研究所 | A kind of application of blended porous membrane in flow battery |
| CN106964264A (en) * | 2017-04-27 | 2017-07-21 | 苏州捷尔沃科技有限公司 | Self-supporting with superhydrophobic breathable property and the pvdf membrane containing substrate |
| US11667782B2 (en) | 2020-09-09 | 2023-06-06 | Industrial Technology Research Institute | Polyvinylidene fluoride film composition, and polyvinylidene fluoride isolation film |
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Open date: 20100512 |