CN1586702A - Method for preparing nano filter membrane using surface crafting technology - Google Patents
Method for preparing nano filter membrane using surface crafting technology Download PDFInfo
- Publication number
- CN1586702A CN1586702A CN 200410053257 CN200410053257A CN1586702A CN 1586702 A CN1586702 A CN 1586702A CN 200410053257 CN200410053257 CN 200410053257 CN 200410053257 A CN200410053257 A CN 200410053257A CN 1586702 A CN1586702 A CN 1586702A
- Authority
- CN
- China
- Prior art keywords
- preparation
- membrane
- technology
- irradiation
- 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.)
- Pending
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to surface grafting process of preparing hydrophilic nanofiltering film. The surface grafting process is one radiation grafting process, which is low temperature plasma radiation process, ultraviolet radiation process, high energy ray radiation process, etc. The present invention has simple operation, controllable reaction, regulation of separating membrane performance in great range and other features, and is especially suitable for the preparation of hydrophilic nanofiltering film.
Description
Technical field
The invention relates to a kind of method for preparing the hydrophily NF membrane with the surface grafting technology.Have characteristics such as simple to operate, that grafting efficiency is high, the performance of film can be regulated in a big way, be specially adapted to the preparation of hydrophily NF membrane.
Background technology
NF membrane is a kind of pressure-actuated diffusion barrier of using, and it is low to have an operating pressure, and advantage such as permeation flux is big has been widely used in separating of the less compound of water treatment and relative molecular mass, is a kind of isolation technics with applications well prospect.
At present, the method for industrial production NF membrane mainly contains interface polycondensation and phase transition method.Though these methods are used widely, also come with some shortcomings.For example the method for interfacial polycondensation has strict requirement to the composition of monomer, the technical difficulty height of polymerisation, and product quality is wayward; And it is often relatively poor with the NF membrane permeability of phase transition method preparation.In addition, all relatively poor with the film hydrophily that these methods are made, the application of film is very limited.
Summary of the invention
It is easy to the objective of the invention is to propose a kind of operation sequence, and product quality is the NF membrane preparation method of control easily, and makes the NF membrane of preparation have good hydrophilicity and permeability.
The NF membrane preparation method that the present invention proposes is a kind of method of surface grafting.Specifically be to existing milipore filter, adopt the surface grafting technology,, connect required monomer, obtain NF membrane through graft reaction.
The present invention adopts the method for surface grafting, can the character of NF membrane can be changed within a large range by changing the chemical analysis and the grafting condition of grafted monomers.The NF membrane of making in this way not only has good hydrophily, and very high permeability is arranged and to the rejection of high price salt.Among the present invention, used milipore filter can obtain from commercially available or self-control.
Surface grafting method of the present invention mainly is meant the method for irradiation grafting, comprises ultraviolet irradiation, low temperature plasma irradiation or high-energy ray irradiation etc.Because the equipment of ultraviolet irradiation is simple, reaction is control easily, therefore is particularly suitable for the present invention.
According to the present invention, the polymer property that the preparation milipore filter is used has certain influence to the preparation of NF membrane.Being particularly suitable for milipore filter material of the present invention is the polymer that main chain or side chain have carbonyl or sulfonyl, as polysulfones (PS), polyether sulfone (PES), polyether-ketone (PEK), contains the polyether-ketone (PEK-C) of phenolphthalein base and polyether sulfone (PES-C) etc.Also can be the blend or the copolymer of above-mentioned polymer.
According to the present invention, the molecular cut off of above-mentioned milipore filter needs less than 200,000, preferably less than 100,000 film.
According to the present invention, all olefinic monomers that can be used for the photochemistry grafting can both be suitable for method of the present invention and prepare NF membrane.Wherein, the monomer that is suitable for preparing the hydrophily NF membrane mainly is to contain carboxyl, amido, hydroxyl and sulfonic compound.Particularly acrylic acid and derivative thereof are as acrylic acid (AA), methacrylic acid (MAA), acrylamide, hydroxyethyl methacrylate etc. (HEMA).Its general formula is
R-CH
2＝C(R’)-COOR”
R=C wherein
nH
2n+1, n≤15; R '=H or CH
3OR "=OH, OCH
2CH
2OH or NH
2Deng.
Contain sulfonic monomer and mainly contain ALS (SAS), methacrylic acid-3-potassium sulfonate propyl ester (SPMA) and 2-acrylamide-2-methyl propane sulfonic acid (AMPS) etc.
According to the present invention, in use, need above-mentioned monomer is dissolved in the corresponding solvent, solvent commonly used is water or alcohols, as methyl alcohol or ethanol.The weight percent concentration of monomer solution is 0.5%～50%.Best 0.5%～20% (weight).
According to the present invention, milipore filter can soak with above-mentioned solution in advance, carries out the ultraviolet irradiation grafting then.Also can in suitable reactor, solution be placed on the film of question response, carry out irradiation grafting again.About 0.1～the 2cm of the thickness of solution.Before graft reaction, with nitrogen to the solution bubbling, to remove the oxygen in the solution.
According to the present invention, the ultraviolet irradiation light source can adopt a kind of low pressure mercury lamp.The power of mercury lamp can be selected between 100W～1000W, and optimum power is 300W～800W.After the power of light source was selected, exposure light intensity can be regulated by the distance that changes between graft copolymer membrane and the light source.Irradiation distance is 0.5cm～50cm.Graft reaction is at normal temperatures, carries out under nitrogen protection.
The performance of NF membrane prepared in accordance with the present invention can also be controlled by changing exposure time.Exposure time can change between 0.5 minute～120 minutes.After reaction finished, the NF membrane of making was used the distilled water rinsing several times, to remove unreacted hydrophilic monomer.
The separating property of NF membrane prepared in accordance with the present invention is to carry out in diameter is the stainless steel osmotic cell of 5cm.Probe temperature is a room temperature, and operating pressure is 0.4MPa～0.8MPa.Permeability of the membrane is used in the pure water flux of film under this condition or is having the water flux in the presence of the salt to represent (unit: kg/m
2.h); The selectivity of film is 1% NaCl or Na to concentration with film
2SO
4The rejection of solution characterizes.Concrete data are seen embodiment.
The specific embodiment
Embodiment 1:
The used milipore filter of present embodiment is to be prepared from the method that changes mutually with the polyether ketone resin (PEK-C) that contains the phenolphthalein base, and the molecular cut off of film is 10,000.
The surface grafting polymerization reaction is what to carry out in the tetrafluoroethene garden shaped reaction device that a diameter is 5cm.Reactor head is equipped with a quartz glass lid.The face of milipore filter is installed in the reactor up, adds the high monomer solution of about 5mm on the surface of film then.Reactor place straight shape uviol lamp source under, uviol lamp power is 300W.Distance between reactor and uviol lamp source is 5cm.
The used monomer solution of present embodiment is that concentration is acrylic acid (AA) aqueous solution of 10% (weight).Exposure time is 1min.After irradiation finishes, with distilled water with Modified Membrane repeatedly rinsing repeatedly, to remove unreacted AA.The pure water flux of AA modified PE KC NF membrane under 0.8MPa that makes is 25.4kg/m
2H is 1% NaCl and Na to concentration
2SO
4The water flux of solution is respectively 23.2kg/m
2H and 20.7kg/m
2H is respectively 65% and 95.7% to the rejection of above-mentioned two kinds of salt.
Embodiment 2:
Press the condition of embodiment 1, the employing molecular cut off is 70,000 PEK-C milipore filter.Irradiation distance is 7cm, and exposure time is 10min.
The flux of gained AA modified PE K-C NF membrane water under 0.8MPa is 2.8kg/m
2H is 1% NaCl and Na to concentration
2SO
4The water flux of solution is respectively 2.72kg/m
2H and 2.53kg/m
2H is respectively 55% and 94.2% to the rejection of above-mentioned two kinds of salt.
Embodiment 3:
Press the condition of embodiment 1, the employing molecular cut off is 30,000 PEK-C milipore filter.Uviol lamp power is 500W.Irradiation distance is 7cm.Monomer solution is the AA aqueous solution of 10% (weight), and exposure time is 5min.
The flux of resulting AA modified PE KC NF membrane water under 0.8MPa is 10.8kg/m
2H is 1% NaCl and Na to concentration
2SO
4The water flux of solution is respectively 8.72kg/m
2H and 8.13kg/m
2H is respectively 56% and 96.2% to the rejection of above-mentioned two kinds of salt.
Embodiment 4:
Press the condition of embodiment 1, the employing molecular cut off is 10,000 poly (ether-sulfone) ultrafiltration membrane.Irradiation distance is 7cm.Monomer solution is the MAA aqueous solution of 10% (weight), and exposure time is 3min,
The flux of resulting AA modified poly (ether-sulfone) NF membrane water under 0.8MPa is 15.4kg/m
2H is 1% NaCl and Na to concentration
2SO
4The water flux of solution is respectively 33.2kg/m
2H and 12.7kg/m
2H is respectively 43% and 92.7% to the rejection of above-mentioned two kinds of salt.
Embodiment 5:
Press the condition of embodiment 1, the employing molecular cut off is 30,000 polysulphone super-filter membrane.Irradiation distance is 11cm.Monomer solution is the allyl sulphonic acid sodium water solution of 10% (weight), and exposure time is 30min,
The flux of polysulfones NF membrane water under 0.4MPa of resulting SAS modification is 60.8kg/m
2H is 1% NaCl and Na to concentration
2SO
4The water flux of solution is respectively 58.1kg/m
2H and 52.63kg/m
2H is respectively 36% and 90.1% to the rejection of above-mentioned two kinds of salt.
Embodiment 6:
Press the condition of embodiment 1, the employing molecular cut off is 70,000 PEK-C milipore filter.Irradiation distance is 7cm.Exposure time is 10min.Predose, film soaks 24hr in the 5%AA aqueous solution.
The flux of PEK-C film water under 0.4MPa of resulting AA modification is 42.8kg/m
2H is 1% NaCl and Na to concentration
2SO
4The water flux of solution is respectively 40.2kg/m
2H and 39.1kg/m
2H is respectively 58% and 92.8% to the rejection of above-mentioned two kinds of salt.
Claims (12)
1, a kind of preparation method of NF membrane is characterized in that existing milipore filter, adopts the surface grafting technology, connects required monomer, obtains NF membrane.
2, preparation method according to claim 1, the molecular cut off that it is characterized in that used milipore filter is less than 200,000.
3, preparation method according to claim 2 is characterized in that used milipore filter material is that main chain or side chain have carbonyl, or the polymer of sulfonyl.
4, preparation method according to claim 1 is characterized in that described surface grafting technology is the surface irradiation crosslinking technology, comprises ultraviolet irradiation technology, low temperature plasma irradiation technique and high-energy ray irradiation technology.
5, preparation method according to claim 4 is characterized in that irradiation bomb is a low pressure mercury lamp, and its power is 100～1000W.
6, preparation method according to claim 4 is characterized in that the distance of irradiation bomb and film is adjustable in 0.5cm～50cm.
7,, it is characterized in that exposure time is 0.5 to assign to 120 minutes according to claim 5 or 6 described preparation methods.
8, preparation method according to claim 1 is characterized in that described grafted monomers is to contain carboxyl, amido, hydroxyl and sulfonic compound.
9, preparation method according to claim 8 is characterized in that used grafted monomers is acrylic acid and derivative thereof, and its general formula is
R-CH
2＝C(R’)-COOR”
R=C wherein
nH
2n+1, n≤15; R '=H or CH
3OR "=OH, OCH
2CH
2OH or NH
2
10, preparation method according to claim 8 is characterized in that described to contain sulfonic monomer be ALS, methacrylic acid-3-potassium sulfonate propyl ester and 2-acrylamide-2-methyl propane sulfonic acid.
11, preparation method according to claim 1 is characterized in that described grafted monomers water or alcohol for solvent, are mixed with corresponding solution, and the weight percent concentration of solution is 0.5%～50%.
12, preparation method according to claim 11; it is characterized in that graft reaction is to carry out in the tetrafluoroethene reactor that the top has quartz glass to cover: film device in reactor, is covered the monomer solution for preparing in the above, and the thickness of solution is 0.1cm～2cm; normal temperature, nitrogen protection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410053257 CN1586702A (en) | 2004-07-29 | 2004-07-29 | Method for preparing nano filter membrane using surface crafting technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410053257 CN1586702A (en) | 2004-07-29 | 2004-07-29 | Method for preparing nano filter membrane using surface crafting technology |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1586702A true CN1586702A (en) | 2005-03-02 |
Family
ID=34602792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410053257 Pending CN1586702A (en) | 2004-07-29 | 2004-07-29 | Method for preparing nano filter membrane using surface crafting technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1586702A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934204A (en) * | 2010-09-17 | 2011-01-05 | 南京林业大学 | Amphoteric charged nanofiltration membrane and preparation method thereof |
| CN101934205A (en) * | 2010-09-17 | 2011-01-05 | 南京林业大学 | Method for preparing amphoteric charged nanofiltration membrane |
| CN101966433A (en) * | 2010-09-19 | 2011-02-09 | 吴大宇 | Hydrophilic modification method of ultrafiltration membrane |
| CN102068912A (en) * | 2010-12-07 | 2011-05-25 | 天津工业大学 | Method for preparing negatively charged nanofiltration membrane through grafting induced after plasma radiation |
| CN101351337B (en) * | 2005-12-30 | 2011-07-27 | 3M创新有限公司 | Functional substrate |
| CN102836646A (en) * | 2012-08-29 | 2012-12-26 | 南京林业大学 | Hydrophilic composite nanofiltration membrane and preparation method thereof |
| CN102836647A (en) * | 2012-08-29 | 2012-12-26 | 南京林业大学 | Preparation method for positively-charged nanofiltration membrane |
| CN103071395A (en) * | 2013-02-01 | 2013-05-01 | 北京碧水源膜科技有限公司 | Dynamic preparation method of ultra-low pressure charge nanometer filtration membrane |
| CN103599703A (en) * | 2013-11-08 | 2014-02-26 | 江南大学 | Nonionic surface modification method of support-free porous high-polymer separation membrane by ultraviolet (UV) curing |
| CN103599704A (en) * | 2013-11-08 | 2014-02-26 | 江南大学 | Anionic surface modification method of support-free porous separation membrane by ultraviolet (UV) curing |
| CN104258747A (en) * | 2014-03-04 | 2015-01-07 | 上海大学 | Method for preparing nylon-66 grafted crylic acid by electronic beam pre-irradiation |
| CN106186545A (en) * | 2016-08-19 | 2016-12-07 | 董金萍 | A kind of new membrane bioreactor sewage water processing means |
| CN107290339A (en) * | 2017-07-21 | 2017-10-24 | 深圳大学 | It is a kind of to be used to detect identification film of water body cadmium ion and preparation method thereof, application |
| CN109092068A (en) * | 2018-10-08 | 2018-12-28 | 湖北中泉环保技术有限公司 | A kind of ultrafiltration membrane preparation method |
| CN109796300A (en) * | 2018-12-29 | 2019-05-24 | 浙江巨化技术中心有限公司 | A kind of continuous preparation method of 2,3,3,3- tetrafluoropropene |
| CN110075711A (en) * | 2019-05-06 | 2019-08-02 | 埃姆媞（无锡）分离技术有限公司 | A kind of big flux height retention specific complex nanofiltration membrane |
| CN110152507A (en) * | 2019-06-06 | 2019-08-23 | 闽江学院 | A kind of preparation method of the self-cleaning polymer porous membrane of surface grafting mixed polymer brush |
-
2004
- 2004-07-29 CN CN 200410053257 patent/CN1586702A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101351337B (en) * | 2005-12-30 | 2011-07-27 | 3M创新有限公司 | Functional substrate |
| CN101934205A (en) * | 2010-09-17 | 2011-01-05 | 南京林业大学 | Method for preparing amphoteric charged nanofiltration membrane |
| CN101934204B (en) * | 2010-09-17 | 2012-09-12 | 南京林业大学 | Amphoteric charged nanofiltration membrane and preparation method thereof |
| CN101934204A (en) * | 2010-09-17 | 2011-01-05 | 南京林业大学 | Amphoteric charged nanofiltration membrane and preparation method thereof |
| CN101966433A (en) * | 2010-09-19 | 2011-02-09 | 吴大宇 | Hydrophilic modification method of ultrafiltration membrane |
| CN101966433B (en) * | 2010-09-19 | 2012-09-26 | 大连先路科技发展有限公司 | Hydrophilic modification method of ultrafiltration membrane |
| CN102068912A (en) * | 2010-12-07 | 2011-05-25 | 天津工业大学 | Method for preparing negatively charged nanofiltration membrane through grafting induced after plasma radiation |
| CN102836646A (en) * | 2012-08-29 | 2012-12-26 | 南京林业大学 | Hydrophilic composite nanofiltration membrane and preparation method thereof |
| CN102836647A (en) * | 2012-08-29 | 2012-12-26 | 南京林业大学 | Preparation method for positively-charged nanofiltration membrane |
| CN103071395B (en) * | 2013-02-01 | 2015-08-19 | 北京碧水源膜科技有限公司 | A kind of dynamic preparation method of ultralow pressure charged nanofiltration membrane |
| CN103071395A (en) * | 2013-02-01 | 2013-05-01 | 北京碧水源膜科技有限公司 | Dynamic preparation method of ultra-low pressure charge nanometer filtration membrane |
| CN103599703A (en) * | 2013-11-08 | 2014-02-26 | 江南大学 | Nonionic surface modification method of support-free porous high-polymer separation membrane by ultraviolet (UV) curing |
| CN103599704A (en) * | 2013-11-08 | 2014-02-26 | 江南大学 | Anionic surface modification method of support-free porous separation membrane by ultraviolet (UV) curing |
| CN104258747A (en) * | 2014-03-04 | 2015-01-07 | 上海大学 | Method for preparing nylon-66 grafted crylic acid by electronic beam pre-irradiation |
| CN106186545A (en) * | 2016-08-19 | 2016-12-07 | 董金萍 | A kind of new membrane bioreactor sewage water processing means |
| CN107290339A (en) * | 2017-07-21 | 2017-10-24 | 深圳大学 | It is a kind of to be used to detect identification film of water body cadmium ion and preparation method thereof, application |
| CN109092068A (en) * | 2018-10-08 | 2018-12-28 | 湖北中泉环保技术有限公司 | A kind of ultrafiltration membrane preparation method |
| CN109796300A (en) * | 2018-12-29 | 2019-05-24 | 浙江巨化技术中心有限公司 | A kind of continuous preparation method of 2,3,3,3- tetrafluoropropene |
| CN110075711A (en) * | 2019-05-06 | 2019-08-02 | 埃姆媞（无锡）分离技术有限公司 | A kind of big flux height retention specific complex nanofiltration membrane |
| CN110075711B (en) * | 2019-05-06 | 2021-10-08 | 埃姆媞（无锡）分离技术有限公司 | Large-flux high-interception special composite nanofiltration membrane |
| CN110152507A (en) * | 2019-06-06 | 2019-08-23 | 闽江学院 | A kind of preparation method of the self-cleaning polymer porous membrane of surface grafting mixed polymer brush |
| CN110152507B (en) * | 2019-06-06 | 2021-07-27 | 闽江学院 | Preparation method of self-cleaning polymer porous membrane with surface grafted with mixed polymer brush |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1586702A (en) | Method for preparing nano filter membrane using surface crafting technology | |
| CN1803265A (en) | Method for preparing nanometer filter membrane using irradiating surface and copolymerized grafting technology | |
| WO2014136697A1 (en) | Functional polymer membrane, manufacturing method therefor, ion exchange membrane and proton conducting membrane equipped with functional polymer membrane, and ion exchange device | |
| Liu et al. | Improving the hydrophilicity of poly (vinylidene fluoride) porous membranes by electron beam initiated surface grafting of AA/SSS binary monomers | |
| Bhattacharya et al. | Grafting: a versatile means to modify polymers: techniques, factors and applications | |
| CN1858090A (en) | Method for hydrophilic modifying of poly-vinylidene fluoride film | |
| KR100562050B1 (en) | New crosslinked polyvinyl alcohol-based membranes and their Preparation Process | |
| CN101934205A (en) | Method for preparing amphoteric charged nanofiltration membrane | |
| CN101934204B (en) | Amphoteric charged nanofiltration membrane and preparation method thereof | |
| Xi et al. | Modification of polytetrafluoroethylene porous membranes by electron beam initiated surface grafting of binary monomers | |
| JP5893578B2 (en) | Functional composite membrane and method for producing the same, ion exchange membrane and proton conducting membrane provided with functional composite membrane | |
| CN103480286A (en) | Preparation method for UV-induced photografted charged nanofiltration membrane and product thereof, and application of product | |
| CN1304096C (en) | Method for hydrophilic modification of ultrahigh molecular weight polyethylene microporous membrane surface | |
| CN1266198C (en) | Method for making PH value-sensitive polyvinylidene fluoride hollow fibre intelligent film and products thereby | |
| Zheng et al. | Synthesis of chitosan–gelatin molecularly imprinted membranes for extraction of L-tyrosine | |
| KR101759998B1 (en) | Ion-exchange polymer containing catechol group, preparation method and application thereof | |
| CN1481928A (en) | hydrophilic organic-inorganic compounded pervaporation separating film and method for making the same | |
| Sangermano et al. | New developments in cationic photopolymerization: process and properties | |
| Hageman et al. | Photoinitiators and photoinitiation, 9 Photoinitiators for radical polymerization which counter oxygen‐inhibition | |
| Reddy et al. | Preparation of strong acid cation-exchange membrane using radiation-induced graft polymerisation | |
| CN102836647A (en) | Preparation method for positively-charged nanofiltration membrane | |
| JPH0786126B2 (en) | Polymer having betaine structure, solution diffusion film, method for producing the same, and use thereof | |
| CN102836648A (en) | Method for preparing zwitter ion-containing positively-charged nanofiltration membrane | |
| JPS62254807A (en) | Production of solution diffusion membrane | |
| CN1056856C (en) | High-temp. resistance and antisalt water-soluble optical polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |