CN100577269C - Method for preparing polyaniline and nano-fibre blend composite film - Google Patents
Method for preparing polyaniline and nano-fibre blend composite film Download PDFInfo
- Publication number
- CN100577269C CN100577269C CN200710060131A CN200710060131A CN100577269C CN 100577269 C CN100577269 C CN 100577269C CN 200710060131 A CN200710060131 A CN 200710060131A CN 200710060131 A CN200710060131 A CN 200710060131A CN 100577269 C CN100577269 C CN 100577269C
- Authority
- CN
- China
- Prior art keywords
- nano
- polyaniline
- composite film
- fibre
- poly
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a preparation method of poly-aniline nano-fibre co-mixing composite film, belonging to the preparation technique of ultra-filter composite film. The method process comprises that poly-aniline nano-fibre is dispersed to one or more out of solvent N, N-dimethylacetamide, dimethylformamide, N-cymene-2-pyrazolidinone or dimethyl sulfoxide; film-forming polymer material polysulfone is uniformly dissolved into the dispersion of the poly-aniline nano-fibre-solvent to gain casting solution; the casting solution is scraped on a glass plate and the film is formed by using water as coagulation bath, so as to gain the poly-aniline nano-fibre co-mixing composite film of the invention with high throughput and high pollution resistance. The preparation method of the poly-aniline nano-fibre co-mixing composite film has simple method, easy operation and low cost; the pure water throughput of the prepared poly-aniline nano-fibre co-mixing composite film is 1.6 to 2.3 times of that of pure polysulfone membrane and the throughput preservation rate of the poly-aniline nano-fibre co-mixing composite film on protein solution is 1.2 to1.5 times of that of the pure polysulfone membrane.
Description
Technical field
The present invention relates to a kind of preparation method of polyaniline and nano-fibre blend composite film, belong to the technology of preparing of ultrafiltration composite membrane.
Background technology
At present, industrial application is membrane material polysulfones (PS) more widely, have characteristics such as better chemical stability, mechanical performance, heat-resisting, acid-proof alkaline, but it is difficult to take into account aspects such as high flux, high rejection and high resistance film pollution, and therefore the modification at the PS membrane material has become the research focus.Present method of modifying mainly contains surface chemical reaction modification, plasma modification, irradiation grafting modification, surfactant-modified, blending and modifying etc.Blending and modifying wherein, method is easy, is easy to control, and membrane stability is good, can keep the characteristics separately of multiple polymers simultaneously, and modified effect is obvious.Relevant patent such as Sun Junfen etc. prepare composite membrane (number of patent application: 200610030913) with polysulfones and vinylic polymers (polyacrylonitrile, polyvinyl chloride, Kynoar or polyvinyl alcohol) blend, the composite membrane good biocompatibility that makes, guaranteeing to have higher rate and protein retention under the higher water flux condition.
Some nano materials also are applied to the modification of conventional film material more and more because of hydrophily of itself and high characteristics such as specific surface energy.By nano material and polymer's mixing treatment are equipped with diffusion barrier, method is easy, compares nano material with complex methods such as deposition, coatings and is difficult for running off, and improves the stability of film greatly.At present, relevant research work both at home and abroad mainly concentrates on nanometer Al
2O
3, TiO
2, Fe
3O
4, ZrO
2On inorganic nano combined film, and the pattern of nano material mostly is spherical, to organic and be that the research of nano material complex film of one dimension fibre pattern is comparatively rare.Relevant patent such as You Xiudong etc. are with nano anti-biotic material (nano-TiO
2, in the nanometer Ag, nanometer Zn, nanometer Cu one or more) with the compound preparation micro-filtration membrane (number of patent application: 200510051363) of polysulfones blend, it is a kind of inorganic nano combined film, the composite membrane hydrophily improves, remedied the strong shortcoming of PS membrane hydrophobicity, antibiotic, the contamination resistance of composite membrane be improved significantly.
The organic material polyaniline has good environmental stability and heat resistance because of it, and unique protonic acid doping characteristic etc. are widely used as the membrane material of processes such as gas separation, pervaporation and electrodialysis.The polyaniline of nanofiber pattern (PANI) can make by simple chemical oxidization method, and it is with inorganic nano material Al
2O
3, TiO
2Deng high-ratio surface energy and water-wet behavior, have characteristics such as protonic acid doping simultaneously, and the polyaniline of one dimension fibre pattern is contributed to some extent to the formation in duct, film inside and the connectivity between the duct.At present, also do not see the relevant report of other relevant polyaniline nano composite membrane technology researchs.As (Peng Wang such as Peng Wang, K..L.Tan.Preparation andcharacterization of semi-conductive poly (vinylidene fluoride)/polyanline blends andmembranes[J] .Applied Surface Science, 193 (2002): 36-45) polyaniline and polyvinylidene blending are prepared composite membrane, belong to mixing between polyaniline and the Kynoar molecule, do not belong to the category of nano composite membrane.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyaniline and nano-fibre blend composite film.This inventive method process is simple, easy to implement, and cost is low, and the polyaniline and nano-fibre blend composite film that makes has high osmosis and selectivity, and has high antifouling property simultaneously.
The present invention is realized by following technical proposals, a kind of preparation method of polyaniline and nano-fibre blend composite film.It is characterized in that comprising following process:
1. polyaniline nano fiber is dispersed in solvent N, the N-dimethylacetylamide, dimethyl formamide, N-methyl-2-pyridine alkane ketone, or in the dimethyl sulfoxide (DMSO) one or more, adopt magnetic agitation and ultrasonic decentralized photo combination, dispersion treatment 2～3 hours, be mixed with mass concentration and be 0.1～2.7% polyaniline nano fiber dispersion liquid, by the mass ratio of polyaniline nano fiber and polysulfones is to add polysulfones again in the dispersion liquid of above-mentioned polyaniline nano fiber-solvent in 1: 100～15: 100, after stirring and dissolving is complete, leave standstill more than 8 hours and remove bubble, obtain casting solution.
2. be 15～30 ℃ in environment temperature, envionmental humidity is 25～70%, and with casting solution striking film forming on glass plate, control casting solution thickness is at 150～350 μ m, and the prevapourising time is 15～120 seconds in the air.Behind prevapourising it being immersed temperature is in 15～30 ℃ of deionized water coagulating baths, leaves standstill more than 4 hours, obtains polyaniline and nano-fibre blend composite film.
The inventive method process is simple, and is easy to implement, and cost is low, and the polyaniline and nano-fibre blend composite film hydrophily of preparation is better, and the preventing membrane pollution ability is improved.The pure water flux of the polyaniline and nano-fibre blend composite film that makes under 0.16MPa is 269～401L/ (m
2H), be 1.6～2.3 times of pure PS membrane.Polyaniline and nano-fibre blend composite film is 96～99% to the rejection of bovine serum albumin(BSA) BSA, and the flux retention rate is 70～82%, is 1.2～1.5 times of pure PS membrane flux retention rate.And polyaniline and nano-fibre blend composite film is easy cleaning more, and after the simple flushing of pure water, the flux recovery rate of nano composite membrane is 73～89%, is 1.2～1.6 times of pure PS membrane flux recovery rate.
Description of drawings
Fig. 1 is the profile scanning electromicroscopic photograph of embodiment 1 prepared polyaniline and nano-fibre blend composite film.
Fig. 2 is the local magnified sweep electromicroscopic photograph at polyaniline and nano-fibre blend composite film section structure I position among Fig. 1.
The specific embodiment
Embodiment 1
(1) gets concentrated hydrochloric acid 8.47ml, be diluted to 100ml, preparation 1M hydrochloric acid solution with deionized water; Measure 2.92ml aniline and be dissolved in the 1M hydrochloric acid solution of 100ml, be made into the hydrochloric acid solution of 0.32M aniline, note is made solution A; Get in the 1M hydrochloric acid solution that the 1.824g ammonium persulfate is dissolved in 100ml equally, be made into the hydrochloric acid solution of the ammonium persulfate of 0.32M, note is made solution B; With A, B two solution rapid mixing, shook 30 seconds, left standstill 4～6 hours; Isolate polyaniline nano fiber with 0.22 μ m miillpore filter suction filtration, clean with deionized water, methyl alcohol, concentrated hydrochloric acid, 25 ℃ of following vacuum drying 4 hours obtain average diameter 43nm, the polyaniline nano fiber of average length 259nm.
(2) take by weighing polyaniline nano fiber 0.15g, place solvent N, among N-dimethylacetylamide (DMAc) 8.35g, under magnetic agitation 100r/min and supersonic frequency 45Hz condition, nanofiber is uniformly dispersed; To polyaniline nano fiber-N, add polysulfones 1.50g in the dispersion liquid of N-dimethylacetylamide, be stirred to dissolving fully, obtain casting solution 10g, leave standstill more than 8 hours, remove bubble in the casting solution; 25 ℃ of temperature, under relative humidity 60% environment, with scraping hymenotome striking film forming on glass plate, controlling diaphragm liquid thickness 300 μ m; After 30 seconds glass plate is dipped in 25 ℃ of deionized waters, leaves standstill more than 4 hours, obtain polyaniline and nano-fibre blend composite film, be dipped in the pure water and preserve.
The polyaniline and nano-fibre blend composite film that makes is under 0.12～0.28MPa, and pure water flux is 305～607L/ (m
2H), to bovine serum albumin(BSA) (BSA, 1000ppm, pH=11) and ovalbumin (AE, 500ppm, pH=11) rejection is respectively 98.6% and 93.4%, through the 90min ultrafiltration (BSA, 1000ppm, pH=11), the flux retention rate of polyaniline and nano-fibre blend composite film is 72.6%, is 1.26 times of pure PS membrane flux retention rate.The surface of this polyaniline and nano-fibre blend composite film and the stereoscan photograph of section structure are seen accompanying drawing of the present invention.
Embodiment 2
Press step among the embodiment 1 (1) preparation polyaniline nano fiber; Take by weighing polyaniline nano fiber 0.015g, place solvent N, among N-dimethylacetylamide (DMAc) 8.485g, under magnetic agitation 120r/min and supersonic frequency 45Hz condition, nanofiber is uniformly dispersed; To polyaniline nano fiber-N, add polysulfones 1.50g in the dispersion liquid of N-dimethylacetylamide, be stirred to dissolving fully, obtain casting solution 10g, leave standstill more than 8 hours, remove bubble in the casting solution; 25 ℃ of temperature, under relative humidity 60% environment, with scraping hymenotome striking film forming on glass plate, controlling diaphragm liquid thickness 300 μ m; After 30 seconds glass plate is dipped in 25 ℃ of deionized waters, leaves standstill more than 4 hours, obtain polyaniline and nano-fibre blend composite film, be dipped in the pure water and preserve.
The polyaniline nano fiber composite membrane that makes is under 0.12～0.28MPa, and pure water flux is 206～467L/ (m
2H), to bovine serum albumin(BSA) (BSA, 1000ppm, pH=11) and ovalbumin (AE, 500ppm, pH=11) rejection is respectively 98.0% and 94.4%, through the 90min ultrafiltration (BSA, 1000ppm, pH=11), the flux retention rate of polyaniline and nano-fibre blend composite film is 81.4%, is 1.48 times of pure PS membrane flux retention rate.
Embodiment 3
Press step among the embodiment 1 (1) preparation polyaniline nano fiber; Take by weighing polyaniline nano fiber 0.12g, place solvent dimethyl formamide 8.68g, under magnetic agitation 150r/min and supersonic frequency 45Hz condition, nanofiber is uniformly dispersed; In the dispersion liquid of polyaniline nano fiber-dimethyl formamide, add polysulfones 1.20g, be stirred to dissolving fully, obtain casting solution 10g, leave standstill more than 8 hours, remove bubble in the casting solution; 24 ℃ of temperature, under relative humidity 45% environment, with scraping hymenotome striking film forming on glass plate, controlling diaphragm liquid thickness 300 μ m; After 30 seconds glass plate is dipped in 24 ℃ of deionized waters, leaves standstill more than 4 hours, obtain polyaniline and nano-fibre blend composite film, be dipped in the pure water and preserve.
The polyaniline and nano-fibre blend composite film that makes is under 0.12～0.28MPa, and pure water flux is 344～689L/ (m
2H), to bovine serum albumin(BSA) (BSA, 1000ppm, pH=11) and ovalbumin (AE, 500ppm, pH=11) rejection is respectively 96.4% and 89.1%, through the 90min ultrafiltration (BSA, 1000ppm, pH=11), the flux retention rate of polyaniline and nano-fibre blend composite film is 75.6%, is 1.37 times of pure PS membrane flux retention rate.
Embodiment 4
Preparation polyaniline nano fiber step is identical with embodiment 2 with the preparation casting solution; The knifing condition is: 24 ℃ of temperature, under relative humidity 50% environment, with scraping hymenotome striking film forming on glass plate, controlling diaphragm liquid thickness 200 μ m; After 30 seconds glass plate is dipped in 25 ℃ of deionized waters, leaves standstill more than 4 hours, obtain polyaniline and nano-fibre blend composite film, be dipped in the pure water and preserve.
The polyaniline and nano-fibre blend composite film that makes is under 0.12～0.28MPa, and pure water flux is 309～712L/ (m
2H), to bovine serum albumin(BSA) (BSA, 1000ppm, pH=11) and ovalbumin (AE, 500ppm, pH=11) rejection is respectively 96.0% and 89.3%, through the 90min ultrafiltration (BSA, 1000ppm, pH=11), the flux retention rate of polyaniline and nano-fibre blend composite film is 80.2%, is 1.46 times of pure PS membrane flux retention rate.
Claims (1)
1. the preparation method of a polyaniline and nano-fibre blend composite film is characterized in that comprising following process:
1) polyaniline nano fiber is dispersed in solvent N, in in N-dimethylacetylamide, the dimethyl formamide one or both, adopt magnetic agitation and ultrasonic decentralized photo combination, dispersion treatment 2～3 hours, be mixed with mass concentration and be 0.1～2.7% polyaniline nano fiber dispersion liquid, by the mass ratio of polyaniline nano fiber and polysulfones is to add polysulfones again in the polyaniline nano fiber dispersion liquid in 1: 100～15: 100, after stirring and dissolving is complete, leave standstill more than 8 hours and remove bubble, obtain casting solution;
2) it is 15～30 ℃ in environment temperature, envionmental humidity is 25～70%, with casting solution striking film forming on glass plate, control casting solution thickness is at 150～350 μ m, the prevapourising time is 15～120 seconds in the air, behind prevapourising it being immersed temperature is in 15～30 ℃ of deionized water coagulating baths, leaves standstill more than 4 hours, obtains polyaniline and nano-fibre blend composite film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710060131A CN100577269C (en) | 2007-12-24 | 2007-12-24 | Method for preparing polyaniline and nano-fibre blend composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710060131A CN100577269C (en) | 2007-12-24 | 2007-12-24 | Method for preparing polyaniline and nano-fibre blend composite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101274220A CN101274220A (en) | 2008-10-01 |
| CN100577269C true CN100577269C (en) | 2010-01-06 |
Family
ID=39994338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710060131A Expired - Fee Related CN100577269C (en) | 2007-12-24 | 2007-12-24 | Method for preparing polyaniline and nano-fibre blend composite film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100577269C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068925B (en) * | 2010-12-08 | 2013-02-06 | 天津大学 | Preparation method of polyaniline nano composite film |
| CN102243203B (en) * | 2011-06-13 | 2014-07-02 | 暨南大学 | Anti-oxidation sensor and preparation method hereof |
| CN102553462B (en) * | 2012-01-11 | 2014-04-16 | 上海理工大学 | Carbon nano tube/polyaniline/polysulfone composite ultra-filtration membrane and preparing method thereof |
| CN102921316A (en) * | 2012-11-07 | 2013-02-13 | 中国海洋大学 | Method for preparing modified polysulfone ultra-filtration membranes through homogeneous ultraviolet light grafting |
| CN104745819B (en) * | 2013-12-27 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | Utilize the method that metal is reclaimed in conducting polymer nanometer spinning from electron wastes |
| CN105833746A (en) * | 2016-06-17 | 2016-08-10 | 安庆市天虹新型材料科技有限公司 | Stain-resistant and weather-resistant polysulfone membrane |
| CN108246115A (en) * | 2018-02-28 | 2018-07-06 | 冯婷婷 | A kind of preparation method of biological detection flat micro-filtration |
| CN112535959A (en) * | 2019-09-23 | 2021-03-23 | 天津工业大学 | Polyaniline-polysulfone modified membrane and preparation method thereof |
| CN112680125B (en) * | 2020-12-28 | 2022-09-23 | 无锡市立帆绝缘材料科技有限公司 | Preparation method of polyaryl fiber-polyester composite film |
| CN113447446B (en) * | 2021-06-28 | 2023-05-05 | 西南大学 | Chip for quantitatively detecting reductive multicomponent biological micromolecules by utilizing oblique incident light reflection difference, application and detection method |
| CN114130286B (en) * | 2021-12-08 | 2024-03-26 | 安徽威能电源科技有限公司 | Lead powder production stirring device of lead-acid storage battery |
| CN114558461A (en) * | 2022-03-21 | 2022-05-31 | 合肥九号线传媒科技有限公司 | Organic-inorganic composite conductive filter membrane and preparation method thereof |
-
2007
- 2007-12-24 CN CN200710060131A patent/CN100577269C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Preparation and characterization ofpolyaniline/polysulfone nanocomposite ultrafiltrationmembrane. Zhifeng Fan, et al.Journal of Membrane Science,Vol.310 . 2007 |
| Preparation and characterization ofpolyaniline/polysulfone nanocomposite ultrafiltrationmembrane. Zhifeng Fan,et al.Journal of Membrane Science,Vol.310. 2007 * |
| 聚苯胺/聚砜复合膜电极对苯二酚及其混合体系的电催化氧化. 冯晓娟等.西北师范大学学报（自然科学版），第43卷第4期. 2007 |
| 聚苯胺/聚砜复合膜电极对苯二酚及其混合体系的电催化氧化. 冯晓娟等.西北师范大学学报(自然科学版)，第43卷第4期. 2007 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101274220A (en) | 2008-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100577269C (en) | Method for preparing polyaniline and nano-fibre blend composite film | |
| CN109847586B (en) | High-flux reverse osmosis membrane and preparation method and application thereof | |
| CN102580560B (en) | Method for preparing nano-material-doped polymer film | |
| CN102068925B (en) | Preparation method of polyaniline nano composite film | |
| CN103418250B (en) | A kind of method at separation membrane surface in-situ preparation nano particle | |
| CN111760461B (en) | Preparation method of polyvinylidene fluoride mixed matrix membrane | |
| CN102389722B (en) | Method for preparing nano composite ultrafiltration membrane by using polyaniline nano material | |
| Wang et al. | Improved poly (vinyl butyral) hollow fiber membranes by embedding multi-walled carbon nanotube for the ultrafiltrations of bovine serum albumin and humic acid | |
| CN1973972A (en) | Prepn process of reinforced hybrid organic-inorganic film | |
| Habibi et al. | Enhanced water flux through ultrafiltration polysulfone membrane via addition‐removal of silica nano‐particles: Synthesis and characterization | |
| CN102091540A (en) | Preparation method of sulfonated polyethersulfone/TiO2 nano composite ultrafiltration membrane | |
| KR101494053B1 (en) | Method for manufacturing asymmetric hollow fiber membrane and asymmetric hollow fiber membrane manufactured using the same | |
| Fang et al. | Evaluating the antifouling properties of poly (ether sulfone)/sulfonated poly (ether sulfone) blend membranes in a full-size membrane module | |
| Ma et al. | Fabrication of antibacterial and self-cleaning CuxP@ g-C3N4/PVDF-CTFE mixed matrix membranes with enhanced properties for efficient ultrafiltration | |
| Zhang et al. | Smart TFC membrane for simulated textile wastewater concentration at elevated temperature enabled by thermal-responsive microgels | |
| CN1597074A (en) | Polyaryl ether sulphone compound separation membrane and its preparation method | |
| CN102512997B (en) | Hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof | |
| KR101944761B1 (en) | Polymeric composition for hydrophilic separation membrane containing sulfonated inorganic particles | |
| CN107670512B (en) | Polyvinylidene fluoride hollow fiber membrane and preparation method thereof | |
| CN104248915A (en) | Preparation method of enhanced flat composite microporous membrane for improving hydrophility | |
| CN102974227B (en) | Method for preparing polymer conductive porous membrane | |
| Wang et al. | Improving the hydrophilicity and antifouling performance of PVDF membranes via PEI amination and further poly (methyl vinyl ether-alt-maleic anhydride) modification | |
| KR101936395B1 (en) | Polymeric composition for hydrophilic separation membrane containing sulfonated inorganic particles | |
| KR101079652B1 (en) | Polymer compound and membrane manufacturing method for membrane bio reactor processing | |
| CN109862958B (en) | Method for producing positively charged membranes |
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: 20100106 Termination date: 20201224 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |