CN104190273A - Preparation method for improving thermosensitivity and hydrophilia of PVDF-g-PNIPAAm membrane - Google Patents
Preparation method for improving thermosensitivity and hydrophilia of PVDF-g-PNIPAAm membrane Download PDFInfo
- Publication number
- CN104190273A CN104190273A CN201410468132.7A CN201410468132A CN104190273A CN 104190273 A CN104190273 A CN 104190273A CN 201410468132 A CN201410468132 A CN 201410468132A CN 104190273 A CN104190273 A CN 104190273A
- Authority
- CN
- China
- Prior art keywords
- pnipaam
- pvdf
- membrane
- film
- casting solution
- 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.)
- Granted
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for improving thermosensitivity and hydrophilia of a PVDF-g-PNIPAAm membrane by changing a membrane formation technology. The method takes PVDF-g-PNIPAAm as a raw material and N,N-dimethylformamide (DMF) as a solvent, tetrahydrofuran (THF) is added into the solvent DMF, the scraped membrane volatilizes for different times before immersed into a coagulating bath to promote the expensive PNIPAAm to enrich on the surface of the membrane, the contents of the PNIPAAm on the surface of the membrane and on the surface of a membrane hole are increased, and the thermosensitivity and the hydrophilia of the copolymer membrane are improved. The method provided by the invention is suitable for the functional modification process of a body of a traditional membrane material; by adding a functional-molecule volatile good solvent into a casting membrane liquid, functional macro-molecules are enriched towards the surface of the membrane in the volatilizing process of the good solvent, and the utilization efficiency of the functional molecules is improved.
Description
[technical field]: the invention belongs to membrane technology field, be specifically related to a kind of PVDF-g-PNIPAAm responsive to temperature film Thermo-sensitive and hydrophilic preparation method of improving.
[background technology]: Kynoar (PVDF) is a kind of crystalline polymer of white powder, density 1.75-1.78g/cm
3its glass transition temperature-39 DEG C, brittle temperature-62 DEG C, crystalline melt temperature is about 170 DEG C, and heat decomposition temperature is more than 315 DEG C, its outstanding characteristic is that mechanical strength is high, ageing-resistant and anti-ultraviolet property is high, the corrosion of the strong oxidizer such as acid and alkali, alkali and halogen under room temperature, is the good separation membrane material of a kind of combination property, and PVDF micro-filtration membrane and milipore filter have been successfully applied to chemical industry, weaving, electronics, the industrial circles such as food, have become the outstanding person in numerous organic polymer membrane materials.
Poly-N-isopropyl acrylamide is a kind of typical large molecule of responsive to temperature.PNIPAAm molecule had both existed hydrophilic amide group, also exist and there is hydrophobic isopropyl group, in this special molecular structure makes it near lowest critical solution temperature (LCST) just, hydrophilic and hydrophobic transformation can occur in the aqueous solution, and strand conformation also can become contraction state by extended configuration.Due to the affect highly significant of temperature on Volume Changes, therefore PNIPAAm is combined with the mode of basement membrane or basal lamina material surface modification or body modification, the film obtaining also can significantly show temperature response performance.The responsive to temperature films that current great majority use are incorporated into PNIPAAm in basement membrane or filmogen exactly, utilize near the conformation transition of PNIPAAm LCST, change hydrophilic and hydrophobic and the membrane pore structure on film surface, thereby reach, to separate the temperature of permeance property controlled.In recent years, in view of the responsive to temperature performance of the good filming performance of PVDF and PNIPAAm, PVDF-g-PNIPAAm copolymer membrane prepared by NIPAAm and Kynoar (PVDF) has obtained research widely.The method that tradition improves the Thermo-sensitive of temperature sensitive film has two kinds, in the process of body modification preparation temperature sensitive membrane, that proportioning by increase NIPAAm in film forming polymer realizes, but NIPAAm is expensive, in film forming polymer inversion of phases film forming procedure, part NIPAAm 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 improves, can stop up a part of fenestra, and chemical reaction takes time and effort, therefore a kind of simple and effective, the method that can more give full play to PNIPAAm effect urgently occurs.
[summary of the invention]: for the deficiencies in the prior art, this patent provides a kind of easy method, forms to improve the method for PVDF-g-PNIPAAm copolymer Thermo-sensitive by changing casting solution.
The present invention, by by the method for adjusting filming technology, improves the content of PVDF-g-PNIPAAm copolymer membrane surface and fenestra surface PNIPAAm, and then improves Thermo-sensitive and the hydrophily of copolymer membrane.In conventional solvent DMF (DMF), add the good solvent of PIPAAm, volatile oxolane (THF) is made into casting solution, leaves standstill a period of time, then use forming film with phase transformation method after knifing in air.In air, in time of repose section, oxolane volatilizees, and in volatilization process, the PNIPAAm molecule in PVDF-g-PNIPAAm can be to film surface enrichment under the drive of THF, and the utilization rate of PNIPAAm is increased.
The technology path that the present invention adopts is:
PVDF-g-PNIPAAm copolymer prepare reference literature [woods is the performance [M] of the synthetic and temperature sensitive film of triumphant .PVDF-g-PNIPAAm copolymer first. Tianjin: Tianjin University of Technology, 2009].
PVDF-g-PNIPAAm, mass ratio is 7: 3-9: 1 DMF and THF mixed solvent, be made into the casting solution of 14wt%-16wt%, deaeration in vacuum drying chamber.After deaeration, casting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leave standstill after 10s-40s, put into coagulating bath, casting solution precipitates formation film gradually, takes out and puts into distilled water and soak, stand-by.
The technical scheme that the present invention solves described product technology problem is: select Kynoar (PVDF) as film forming main material, temperature-responsive polymer NIPA (NIPAAm) is grafted on Kynoar (PVDF), use the mixed solvent of DMF and THF to be made into knifing after casting solution, leave standstill after different time, put into coagulating bath film forming, result shows the prolongation along with time of repose in air, film temperature sensitiveness improves, 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 the volatile good solvent of functional molecular in casting solution, in the process of volatilizing at this good solvent, can impel functionalization molecule to film surface enrichment, improve the utilization ratio of functionalization molecule.
[specific embodiments]:
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 into there-necked flask, adds the DMF of 60ml,, dissolves in backward there-necked flask and passes into N to dissolving by magnetic stirrer
210min, then add the refining NIPAAm of 5g and the refining AIBN of 0.082g as initator, continue to pass into 15minN
2, continue, after reaction 10h, to be poured in large beaker, add 125ml methyl alcohol, precipitation suction filtration, three suction filtrations of three washings, by the copolymer obtaining dry 24h in the baking oven of 60 DEG C.
2) prepare PVDF-g-PNIPAAm copolymer membrane.Take the casting solution that the PVDF-g-PNIPAAm of 1g and pure DMF are made into 15wt%, deaeration 3h in vacuum drying chamber.After deaeration, casting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leave standstill after 10s, put into coagulating bath, casting solution 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, take again mass ratio and 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, casting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leave standstill after 10s, put into coagulating bath, casting solution 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, take again mass ratio and 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, casting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leave standstill after 20s, put into coagulating bath, casting solution 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, take again mass ratio and 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, casting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leave standstill after 30s, put into coagulating bath, casting solution precipitates formation film gradually, puts into distilled water and soaks, stand-by.
Embodiment 5:
1) prepare PVDF-g-PNIPAAm copolymer.With embodiment 1.
2) prepare PVDF-g-PNIPAAm copolymer membrane.Take dry PVDF-g-PNIPAAm copolymer 4g, take again mass ratio and 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, casting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leave standstill after 40s, put into coagulating bath, casting solution precipitates formation film gradually, puts into distilled water and soaks, stand-by.
Claims (4)
1. a preparation method who improves PVDF-g-PNIPAAm film Thermo-sensitive, comprises 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,, dissolves in backward there-necked flask and passes into N to dissolving by magnetic stirrer
210min-15min, then add refining NIPAAm and refining AIBN as initator, continue to pass into N
210min-15min, continues, after reaction 10h-12h, to be poured in large beaker, adds methyl alcohol, precipitation suction filtration, and 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 and pure DMF are made into the casting solution of 14wt%-16wt%, deaeration in vacuum drying chamber, after deaeration, casting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leave standstill after 10s, put into coagulating bath, casting solution precipitates formation film gradually, after 40s by its taking-up, put into distilled water and soak, stand-by;
PVDF-g-PNIPAAm, mass ratio is 7: 3-9: 1 DMF and THF mixed solvent, be made into the casting solution of 14wt%-16wt%, deaeration in vacuum drying chamber, after deaeration, casting solution is poured on glass plate, scrapes the film that thickness is about 0.15mm with glass bar, leave standstill after 10s-40s, put into coagulating bath, casting solution precipitates formation film gradually, takes out and puts into distilled water and soak, stand-by.
2. raising PVDF-g-PNIPAAm film Thermo-sensitive according to claim 1 and hydrophilic preparation method, is characterized in that: this preparation method solvent used is the mixed solvent of DMF and oxolane.
3. raising PVDF-g-PNIPAAm film Thermo-sensitive according to claim 1 and hydrophilic preparation method, is characterized in that: after knifing, in air, standing a period of time is put into coagulating bath film forming again.
4. raising PVDF-g-PNIPAAm film Thermo-sensitive according to claim 1 and hydrophilic preparation method, is characterized in that: oxolane is volatile, and be the solvent of NIPA, and its volatilization process is conducive to PNIPAAm to film surface enrichment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104190273A true CN104190273A (en) | 2014-12-10 |
| CN104190273B CN104190273B (en) | 2016-05-11 |
Family
ID=52075725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410468132.7A Expired - Fee Related CN104190273B (en) | 2014-09-12 | 2014-09-12 | A kind of PVDF-g-PNIPAAm film Thermo-sensitive and hydrophilic preparation method of improving |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104190273B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109382002A (en) * | 2017-08-02 | 2019-02-26 | 浙江工业大学 | A kind of intelligent switch film and preparation method thereof based on nanogel |
| CN112973478A (en) * | 2020-02-25 | 2021-06-18 | 四川大学 | Temperature-sensitive super-hydrophilic membrane and preparation method thereof |
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 |
-
2014
- 2014-09-12 CN CN201410468132.7A patent/CN104190273B/en not_active Expired - Fee Related
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 |
|---|
| 冯霞 等: "凝固浴温度对PVDF-g-PNIPAAm温度敏感膜成膜过程与性能的影响", 《高等学校化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109382002A (en) * | 2017-08-02 | 2019-02-26 | 浙江工业大学 | A kind of intelligent switch film and preparation method thereof based on nanogel |
| CN109382002B (en) * | 2017-08-02 | 2021-06-04 | 浙江工业大学 | Intelligent switch membrane based on nanogel and preparation method thereof |
| CN112973478A (en) * | 2020-02-25 | 2021-06-18 | 四川大学 | Temperature-sensitive super-hydrophilic membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104190273B (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Irregular dot array nanocomposite molecularly imprinted membranes with enhanced antibacterial property: Synergistic promotion of selectivity, rebinding capacity and flux | |
| CN101293185A (en) | Method for producing polyvinylidene fluoride porous membrane | |
| JP6211707B2 (en) | Solvent separation system and method | |
| CN103861480B (en) | The preparation method of a kind of hydrophilic polyvinylidene fluoride flat sheet membrane and hollow-fibre membrane | |
| CN104190273B (en) | A kind of PVDF-g-PNIPAAm film Thermo-sensitive and hydrophilic preparation method of improving | |
| CN104524993A (en) | Cross-linked sulfonated polysulfone/polyether sulfone-sulfonated polysulfone composite membrane and manufacturing method thereof | |
| Wu et al. | An improved process for polyvinylidene fluoride membrane preparation by using a water soluble diluent via thermally induced phase separation technique | |
| CN105289338B (en) | Polyether sulfone/polyvinylidene fluoride blending film with supporting layer and preparation method thereof | |
| CN104383818A (en) | Composite microporous diaphragm, preparation method and application thereof | |
| CN108246130A (en) | A kind of GO/SiO2The preparation method of modified nano compound film | |
| CN102179189A (en) | Preparation method of pollution-resisting polyvinylidene fluoride ultrafiltration membrane | |
| CN102698618B (en) | A kind of polyethersulfone porous membrane for Membrane Materials process and preparation method thereof | |
| CN102489178B (en) | Method for preparing molybdenum disulfide pervaporation membrane for separating alcohol-containing wastewater | |
| CN104056552B (en) | A kind of method for concentration of glue class Chinese medicine | |
| CN103406034B (en) | A kind of preparation method of the polyether block amide microporous barrier for Membrane Materials process | |
| CN103752179A (en) | Preparation method of hydrophobic hollow fiber membrane | |
| CN103285743B (en) | Hydrophilization modification method for polyvinyl chloride alloy ultrafiltration membrane | |
| CN105749765A (en) | Preparation method of high-performance cellulose triacetate forward osmosis membrane | |
| CN106422803A (en) | Preparation method of novel polyamide composite forward osmosis membrane | |
| CN104801202A (en) | Method for preparing distillation film with support body | |
| CN111729520A (en) | Seawater desalination composite membrane for producing hydrogen-rich direct drinking water and preparation method thereof | |
| CN104324621A (en) | High throughput polyvinylidene fluoride flat-sheet film with controllable pore structure, and preparation method thereof | |
| CN104147945A (en) | Method for preparing polyvinylidene fluoride microporous film | |
| CN104190266A (en) | Method for regulating structure and properties of PVDF-g-PNIPAAm copolymer membrane | |
| CN104016462B (en) | A kind of preparation method of reuse water discoloring agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160511 Termination date: 20160912 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |