CN104190273B - A kind of PVDF-g-PNIPAAm film Thermo-sensitive and hydrophilic preparation method of improving - Google Patents
A kind of PVDF-g-PNIPAAm film Thermo-sensitive and hydrophilic preparation method of improving Download PDFInfo
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- CN104190273B CN104190273B CN201410468132.7A CN201410468132A CN104190273B CN 104190273 B CN104190273 B CN 104190273B CN 201410468132 A CN201410468132 A CN 201410468132A CN 104190273 B CN104190273 B CN 104190273B
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Abstract
The invention discloses one and improve PVDF-g-PNIPAAm film Thermo-sensitive and hydrophilic method by changing filming technology. The present invention is taking PVDF-g-PNIPAAm as raw material, N, dinethylformamide (DMF) is solvent, by add oxolane (THF) in solvent DMF, and before the film scraping is immersed in to coagulating bath, volatilization different time, impels expensive PNIPAAm to film surface enrichment, improve the content of film surface and fenestra surface PNIPAAm, increase hydrophily and the temperature sensitivity of copolymer membrane. Method provided by the invention goes for conventional film material to carry out noumenon function modifying process, by add the volatile good solvent of functional molecular in casting solution, in this good solvent volatilization process, can impel functionalized macromolecular to film surface enrichment, improve the utilization ratio of functionalization molecule.
Description
[technical field]: the invention belongs to membrane technology field, be specifically related to a kind of PVDF-g-PNIPAAm of raising temperature quickSense film Thermo-sensitive and hydrophilic preparation method.
[background technology]: Kynoar (PVDF) is a kind of crystalline polymer of white powder, density 1.75-1.78g/cm3, its glass transition temperature-39 DEG C, brittle temperature-62 DEG C, crystalline melt temperature is about 170 DEG C, and thermal decompositionTemperature is more than 315 DEG C, and its outstanding characteristic is that mechanical strength is high, ageing-resistant and anti-ultraviolet property is high, acid and alkali under room temperature,The corrosion of the strong oxidizers such as alkali and halogen, is the good separation membrane material of a kind of combination property, and PVDF micro-filtration membrane and milipore filter areBe successfully applied to chemical industry, weaving, electronics, the industrial circles such as food, have become outstanding in numerous organic polymer membrane materialsPerson.
Poly-N-isopropyl acrylamide is a kind of typical large molecule of responsive to temperature. PNIPAAm molecule had both existed hydrophilicAmide group, also exist and there is hydrophobic isopropyl group, this special molecular structure makes it minimum justNear critical solution temperature (LCST) time, hydrophilic and hydrophobic transformation can occur in the aqueous solution, strand conformation alsoCan become contraction state by extended configuration. Due to the affect highly significant of temperature on Volume Changes, therefore by PNIPAAm and basement membraneOr the mode of basal lamina material surface modification or body modification combines, the film obtaining also can significantly show temperature and ringAnswer performance. The responsive to temperature film that current great majority use is incorporated into PNIPAAm in basement membrane or filmogen exactly, utilizesNear the conformation transition of PNIPAAm LCST, changes hydrophilic and hydrophobic and the membrane pore structure on film surface, thereby reaches separation permeabilityThe temperature of energy is controlled. In recent years, in view of the responsive to temperature performance of the good filming performance of PVDF and PNIPAAm, NIPAAm is with poly-PVDF-g-PNIPAAm copolymer membrane prepared by vinylidene (PVDF) has obtained research widely. Tradition improves the temperature sensitive of temperature sensitive filmThe method of property has two kinds, in the process of body modification preparation temperature sensitive membrane, is by increasing in film forming polymerThe proportioning of NIPAAm realizes, but NIPAAm is expensive, in film forming polymer inversion of phases film forming procedure, and a partNIPAAm is embedded in the middle of film body, does not play a role, and causes wastage of material. Another method is membrane surface modification,By improving the grafting density of NIPAAm on film surface, improve the performance of responsive to temperature film, but grafting density raising can be stopped upPart fenestra, and chemical reaction takes time and effort, therefore a kind of simple and effective, can more give full play to PNIPAAm and doWith method urgently occur.
[summary of the invention]: for the deficiencies in the prior art, this patent provides a kind of easy method, by changing casting filmLiquid forms to improve the method for PVDF-g-PNIPAAm copolymer Thermo-sensitive.
The present invention, by by the method for adjusting filming technology, improves PVDF-g-PNIPAAm copolymer membrane surface and fenestra surfaceThe content of PNIPAAm, and then Thermo-sensitive and the hydrophily of raising copolymer membrane. At conventional solvent DMF(DMF) in, add the good solvent of PIPAAm, volatile oxolane (THF) is made into casting solution, after knifing, in air, leaves standstillA period of time, then use forming film with phase transformation method. In air, in time of repose section, oxolane volatilizees, in volatilization process,PNIPAAm molecule in PVDF-g-PNIPAAm can be to film surface enrichment under the drive of THF, and the utilization rate of PNIPAAm is increasedAdd.
The technology path that the present invention adopts is:
1) prepare PVDF-g-PNIPAAm copolymer
Water-bath is warming up to 50 DEG C-70 DEG C, and the PVDF of alkali treatment is put into there-necked flask, adds DMF, uses magnetic agitationDevice is stirred to dissolving, dissolves in backward there-necked flask and passes into N210min-15min, then add refining NIPAAm and refiningAIBN, as initator, continues to pass into N210min-15min, continues, after reaction 10h-12h, to be poured in large beaker, addsMethyl alcohol, precipitation suction filtration, three suction filtrations of three washings, by the copolymer obtaining dry 24h in the baking oven of 50 DEG C-70 DEG C;
2) prepare PVDF-g-PNIPAAm copolymer membrane
PVDF-g-PNIPAAm, mass ratio is 7: 3-9: 1 DMF and THF mixed solvent, be made into 14wt%-16wt%'sCasting solution, deaeration in vacuum drying chamber, after deaeration, is poured on casting solution on glass plate, scrapes thickness be about with glass barThe film of 0.15mm, leaves standstill after 10s-40s, puts into coagulating bath, and casting solution precipitates formation film gradually, takes out and put into distilled waterMiddle immersion, stand-by.
The technical scheme that the present invention solves described product technology problem is: select Kynoar (PVDF) as film forming masterWant material, temperature-responsive polymer NIPA (NIPAAm) is grafted to Kynoar (PVDF) upper, makeBe made into knifing after casting solution with the mixed solvent of DMF and THF, leave standstill after different time, put into coagulating bath film forming, result showsAlong with the prolongation of time of repose in air, film temperature sensitiveness improves, and hydrophily strengthens, and flux increases.
Raising PVDF-g-PNIPAAm Thermo-sensitive provided by the present invention and hydrophilic method technique are simple, easy to operate,Cost is low, can be adapted to conventional film material to carry out the body modifying process of functionalization, by add function in casting solutionThe volatile good solvent of molecule, in the process of volatilizing at this good solvent, can impel functionalization molecule to film surface enrichment,Improve the utilization ratio of functionalization molecule.
[detailed description of the invention]:
Embodiment 1:
1) prepare PVDF-g-PNIPAAm copolymer. Water-bath is warming up to 60 DEG C, and the PVDF that takes 5g alkali treatment puts intoIn there-necked flask, add the DMF of 60ml,, dissolve in backward there-necked flask and pass into dissolving by magnetic stirrerN210min, then add the refining NIPAAm of 5g and the refining AIBN of 0.082g as initator, continue to pass into 15minN2, continueAfter reaction 10h, be poured in large beaker, add 125ml methyl alcohol, precipitation suction filtration, three suction filtrations of three washings, by being total to of obtainingPolymers is dry 24h in the baking oven of 60 DEG C.
2) prepare PVDF-g-PNIPAAm copolymer membrane. Take dry PVDF-g-PNIPAAm copolymer 4g, then take matterAmount than be the DMF of 7: 3 and THF as solvent, be made into the casting solution of 15wt%, deaeration 3h in vacuum drying chamber, after deaeration, generalCasting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leaves standstill after 10s, puts into coagulating bath, castingFilm liquid precipitates formation film gradually, puts into distilled water and soaks, stand-by.
Embodiment 2:
1) prepare PVDF-g-PNIPAAm copolymer. With embodiment 1.
2) prepare PVDF-g-PNIPAAm copolymer membrane. Take dry PVDF-g-PNIPAAm copolymer 4g, then take matterAmount than be the DMF of 7: 3 and THF as solvent, be made into the casting solution of 15wt%, deaeration 3h in vacuum drying chamber, after deaeration, generalCasting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leaves standstill after 20s, puts into coagulating bath, castingFilm liquid precipitates formation film gradually, puts into distilled water and soaks, stand-by.
Embodiment 3:
1) prepare PVDF-g-PNIPAAm copolymer. With embodiment 1.
2) prepare PVDF-g-PNIPAAm copolymer membrane. Take dry PVDF-g-PNIPAAm copolymer 4g, then take matterAmount than be the DMF of 7: 3 and THF as solvent, be made into the casting solution of 15wt%, deaeration 3h in vacuum drying chamber, after deaeration, generalCasting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leaves standstill after 30s, puts into coagulating bath, castingFilm liquid precipitates formation film gradually, puts into distilled water and soaks, stand-by.
Embodiment 4:
1) prepare PVDF-g-PNIPAAm copolymer. With embodiment 1.
2) prepare PVDF-g-PNIPAAm copolymer membrane. Take dry PVDF-g-PNIPAAm copolymer 4g, then take matterAmount than be the DMF of 7: 3 and THF as solvent, be made into the casting solution of 15wt%, deaeration 3h in vacuum drying chamber, after deaeration, generalCasting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leaves standstill after 40s, puts into coagulating bath, castingFilm liquid precipitates formation film gradually, puts into distilled water and soaks, stand-by.
Claims (1)
1. improve PVDF-g-PNIPAAm film Thermo-sensitive and a hydrophilic method, comprise the steps:
1) prepare PVDF-g-PNIPAAm copolymer
Water-bath is warming up to 50 DEG C-70 DEG C, and the PVDF of alkali treatment is put into there-necked flask, adds DMF, stirs with magnetic stirring apparatusMix to dissolving, dissolve in backward there-necked flask and pass into N210min-15min, then add refining NIPAAm and refining AIBNAs initator, continue to pass into N210min-15min, continue, after reaction 10h-12h, to be poured in large beaker, add firstAlcohol, precipitation suction filtration, three suction filtrations of three washings, by the copolymer obtaining dry 24h in the baking oven of 50 DEG C-70 DEG C;
2) prepare PVDF-g-PNIPAAm copolymer membrane
PVDF-g-PNIPAAm, mass ratio are 7: 3-9: 1 DMF and THF mixed solvent, be made into the casting film of 14wt%-16wt%Liquid, deaeration in vacuum drying chamber, after deaeration, is poured on casting solution on glass plate, and scraping thickness with glass bar is 0.15mm'sFilm, leaves standstill 10s-40s, leaves standstill in process because THF is volatile, and is the solvent of NIPAAm, and its volatilization process is conducive toPNIPAAm, to film surface enrichment, puts into coagulating bath after leaving standstill, and casting solution precipitates formation film gradually, takes out and put into distilled waterMiddle immersion, stand-by.
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| CN201410468132.7A CN104190273B (en) | 2014-09-12 | 2014-09-12 | A kind of PVDF-g-PNIPAAm film Thermo-sensitive and hydrophilic preparation method of improving |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6458303A (en) * | 1984-03-09 | 1989-03-06 | Agency Ind Science Techn | Permeably separating membrane consisting of temperature sensitive film material |
| CN1153483A (en) * | 1994-07-18 | 1997-07-02 | 昆士兰大学 | Method and apparatus for separating liquid-liquid mixtures |
| CN101711950A (en) * | 2009-11-23 | 2010-05-26 | 天津工业大学 | Flat separation membrane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6458303A (en) * | 1984-03-09 | 1989-03-06 | Agency Ind Science Techn | Permeably separating membrane consisting of temperature sensitive film material |
| CN1153483A (en) * | 1994-07-18 | 1997-07-02 | 昆士兰大学 | Method and apparatus for separating liquid-liquid mixtures |
| CN101711950A (en) * | 2009-11-23 | 2010-05-26 | 天津工业大学 | Flat separation membrane |
Non-Patent Citations (1)
| Title |
|---|
| 凝固浴温度对PVDF-g-PNIPAAm温度敏感膜成膜过程与性能的影响;冯霞 等;《高等学校化学学报》;20110630;第32卷;第1424-1430页 * |
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