CN103223308A - Composite nanofiltration membrane prepared based on aliphatic sulfonate condensation product - Google Patents
Composite nanofiltration membrane prepared based on aliphatic sulfonate condensation product Download PDFInfo
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- CN103223308A CN103223308A CN2013101420000A CN201310142000A CN103223308A CN 103223308 A CN103223308 A CN 103223308A CN 2013101420000 A CN2013101420000 A CN 2013101420000A CN 201310142000 A CN201310142000 A CN 201310142000A CN 103223308 A CN103223308 A CN 103223308A
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Abstract
The invention relates to a composite nanofiltration membrane, especially relates to a composite nanofiltration membrane employing an aliphatic sulfonate condensation product as an anion polyelectrolyte. The composite nanofiltration membrane comprises a basal membrane layer and a composite membrane layer in order, and the composite membrane layer is formed by static self assembly of the cation polyelectrolyte and the anion polyelectrolyte, wherein, the anion polyelectrolyte is an aliphatic sulfonate condensation product solution. The aliphatic sulfonate condensation product is used as an anion polyelectrolyte, and compared with the present anion polyelectrolyte and aliphatic sulfonate condensation product has a lower cost, thereby reducing the cost of the prepared composite nanofiltration membrane, and improving the separating performance for Ni2+, Ca2+ divalent metal ions and xylenol orange, rhodamine B and other dye molecules in heavy metal ion waste water and dye waste water by the prepared composite nanofiltration membrane.
Description
Technical field
The present invention relates to a kind of composite nanometer filtering film, relating in particular to a kind of aliphatic sulfonate condensation product that adopts is the composite nanometer filtering film of anionic polyelectrolyte preparation.
Background technology
NF membrane is a kind of new membrane isolation technics between ultrafiltration and counter-infiltration.The preparation of composite nanometer filtering film is better in intensity mostly, the membrane surface that flux is bigger covers one deck selective separation layer as thin as a wafer, its preparation method mainly contains cladding process, phase inversion (as the patent of publication number CN102091539A), interfacial polymerization is (as publication number CN101254419A, CN101559334A, the patent of CN101934201A), the surface grafting method is (as publication number CN102000511A, CN102068912A, the patent of CN1586702A) etc., commercial NF membrane adopts the interfacial polymerization preparation more, and (as publication number is CN102641667A, CN102151499A, the patent of CN1806901A), but these methods are had relatively high expectations to basement membrane, side reaction is many, is difficult to obtain the NF membrane of superthin layer.
Self-assembly method is to utilize the static self-assembly process alternately to assemble polyanion and polycation electrolyte multilayer film as ultra-thin separating layer on basement membrane layer by layer, thereby obtains composite nanometer filtering film.This method technology is simple, film forming matter abundant, be not subjected to the substrate restriction and can effectively control film layer structure, gets more and more people's extensive concerning.At present, the cationic polyelectrolyte of self-assembly method use layer by layer mainly contains polymine, poly-divinyl propyl ammonium chloride, polyvinylamine, poly-N, and the patent of N ' dimethyl diallyl ammonium chloride (as the patent of publication number CN102553461A, CN101274222A, CN101053780A, CN101298026A, CN102580550A), poly-4-vinyl arsenic pyridine (as the patent of publication number CN102688701A), publication number CN1724128A also discloses polyvinyl alcohol, collagen, shitosan and poly-D-lysine etc. as cationic polyelectrolyte solution; And anionic polyelectrolyte mainly contains kayexalate and Sodium Polyacrylate (as publication number CN102553461A, CN101053780A, CN101298026A, the patent of CN102580550A), kayexalate-maleic acid (salt) copolymer (as the patent of publication number CN101274222A), the patent of publication number CN1724128A also discloses the employing polyvinyl sulfonate simultaneously, sulfuric acid glucose sugar, chondroitin sulfate, sodium alginate and polymethylacrylic acid etc. are as anionic polyelectrolyte solution.But never adopt the relevant report of aliphatic sulfonate condensation product as anionic polyelectrolyte solution.
Summary of the invention
At the weak point of above-mentioned technology, the invention provides a kind of is that anionic polyelectrolyte prepares composite nanometer filtering film with the aliphatic sulfonate condensation product.
A kind of composite nanometer filtering film, comprise base membrane layer, polyelectrolyte composite bed successively, described polyelectrolyte composite bed is that cationic polyelectrolyte and anionic polyelectrolyte form through the static self assembly, and wherein, described anionic polyelectrolyte is an aliphatic sulfonate condensation product solution.
Further, described basement membrane is a molecular weight less than 100,000 milipore filter.
Preferably, described basement membrane is polyacrylonitrile ultrafiltration film, cellulose-acetafolic, polysulphone super-filter membrane, aluminium oxide ceramics milipore filter.
Preferably, described cationic polyelectrolyte comprises polymine (PEI), poly-divinyl propyl ammonium chloride (PDDA), polyvinylamine (PVA).
Preferably, described anionic polyelectrolyte comprises sulfonated acetone formaldehyde condensation products, sulfonation cyclohexanone formaldehyde condensation products, sulfonation acetophenone furfural condensation product, sulfonation MEK formaldehyde condensation products.
Beneficial effect of the present invention is, employed anionic polyelectrolyte is the aliphatic sulfonate condensation product, the aliphatic sulfonate condensation product is a class sulfonated ketone aldehyde condensate, it is that carbonyls and aldehyde compound are condensed into the aliphatic macromolecule that forms under proper condition, and open carbonyl by sulfonating reaction, in strand, introduce a family macromolecule condensation product of hydrophily sulfonic acid group, because of introducing hydrophilic sulfonic group in the aliphatic sulfonate condensation product strand, making it can be used as anionic polyelectrolyte uses, and compare existing anionic polyelectrolyte, the cost of aliphatic sulfonate condensation product is lower, reduced the cost of preparation composite nanometer filtering film, the composite nanometer filtering film for preparing simultaneously is to Ni in effluent containing heavy metal ions and the waste water from dyestuff
2+, Ca
2+Dye molecules such as bivalent metal ion and dimethyl phenol orange, rhodamine B all have good separating property.
Description of drawings
Fig. 1 is a flow chart of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
A kind of composite nanometer filtering film comprises base membrane layer, composite film successively, and described composite film is that cationic polyelectrolyte and anionic polyelectrolyte form through the static self assembly, and wherein, described anionic polyelectrolyte is an aliphatic sulfonate condensation product solution.
Further, described basement membrane is a molecular weight less than 100,000 milipore filter.
Preferably, described basement membrane is polyacrylonitrile ultrafiltration film, cellulose-acetafolic, polysulphone super-filter membrane, aluminium oxide ceramics milipore filter.
Preferably, described cationic polyelectrolyte comprises polymine (PEI), poly-divinyl propyl ammonium chloride (PDDA), polyvinylamine (PVA).
Preferably, described anionic polyelectrolyte comprises sulfonated acetone formaldehyde condensation products, sulfonation cyclohexanone formaldehyde condensation products, sulfonation acetophenone furfural condensation product, sulfonation MEK formaldehyde condensation products.
Described composite nanometer filtering film, by the following steps preparation, as shown in Figure 1:
Step 101: with the milipore filter is basement membrane, and it is immersed concentration is in the cationic polyelectrolyte solution of 1.0～10.0mg/mL, takes out behind dipping 10～30min, fully cleans with deionized water;
Step 102: the film that step 101 is obtained is transferred in the aliphatic sulfonate condensation product solution of 1.0～20.0mg/mL, behind dipping 10～30min, takes out, and uses washed with de-ionized water.Described step repeating step can obtain described composite nanometer filtering film 2-8 time.
Embodiment 1
A kind of composite nanometer filtering film prepares as follows:
Step 101: with the polyacrylonitrile ultrafiltration film is basement membrane, and it is immersed concentration is in the polymine polyelectrolyte solution of 10.0mg/mL, takes out behind the dipping 10min, fully cleans with deionized water;
Step 102: the film that step 101 is obtained is transferred in the sulfonation cyclohexanone formaldehyde condensation products solution of 20.0mg/mL, behind the dipping 10min, takes out, and uses washed with de-ionized water.
Repeat above-mentioned steps 2 times, can obtain described composite nanometer filtering film.
Embodiment 2
A kind of composite nanometer filtering film prepares as follows:
Step 101: with the cellulose-acetafolic is basement membrane, and it is immersed concentration is in the polymine polyelectrolyte solution of 1.0mg/mL, takes out behind the dipping 30min, fully cleans with deionized water;
Step 102: the film that step 101 is obtained is transferred in the sulfonation cyclohexanone formaldehyde condensation products solution of 1.0mg/mL, behind the dipping 30min, takes out, and uses washed with de-ionized water.
Repeat above-mentioned steps 8 times, can obtain described composite nanometer filtering film.
Embodiment 3
A kind of composite nanometer filtering film prepares as follows:
Step 101: with the polyacrylonitrile ultrafiltration film is basement membrane, and it is immersed concentration is in the polymine polyelectrolyte solution of 5.0mg/mL, takes out behind the dipping 20min, fully cleans with deionized water;
Step 102: the film that step 101 is obtained is transferred in the sulfonation cyclohexanone formaldehyde condensation products solution of 8.0mg/mL, behind the dipping 15min, takes out, and uses washed with de-ionized water.
Repeat above-mentioned steps 5 times, can obtain described composite nanometer filtering film.
Embodiment 4:
Present embodiment and embodiment 3 are roughly the same, and different is to have increased by 100 steps before step 101, specific as follows:
Step 100: is basement membrane with molecular cut off less than 100,000 the fine milipore filter of polypropylene, with behind the NaOH solution-treated 30min of 2mol/L, spends deionised water to neutral;
Step 101: it is in the polyvinylamine polyelectrolyte solution of 5.0mg/mL that the polyacrylonitrile ultrafiltration film after step 100 processing is immersed concentration, takes out behind the dipping 20min, fully cleans with deionized water;
Step 102: the film that step 101 is obtained is transferred in the sulfonated acetone formaldehyde condensation products solution of 8.0mg/mL, behind the dipping 20min, takes out, and uses washed with de-ionized water.
Repeat above-mentioned steps 6 times, can obtain described composite nanometer filtering film.
Embodiment 5:
Present embodiment and embodiment 4 are roughly the same, and different is the basement membrane difference that adopts in step 100, specific as follows:
Step 100: is basement membrane with molecular cut off less than 100,000 polysulphone super-filter membrane, after fully washing with deionization, soaks 2h;
Step 101: it is in the polymine polyelectrolyte solution of 6.0mg/mL that the polysulphone super-filter membrane after step 100 processing is immersed concentration, takes out behind the dipping 20min, fully cleans with deionized water;
Step 102: the film that step 101 is obtained is transferred in the sulfonation MEK formaldehyde condensation products solution of 8.0mg/mL, behind the dipping 20min, takes out, and uses washed with de-ionized water.
Repeat above-mentioned steps 6 times, can obtain described composite nanometer filtering film.
Embodiment 6:
Present embodiment and embodiment 4 are roughly the same, and different is the basement membrane difference that adopts in step 100, specific as follows:
Step 100: is basement membrane with molecular cut off less than 100,000 aluminium oxide ceramics milipore filter, after fully washing with deionization, soaks 2h;
Step 101: it is in the poly-divinyl propyl ammonium chloride polyelectrolyte solution of 5.0mg/mL that the aluminium oxide ceramics milipore filter after step 100 processing is immersed concentration, takes out behind the dipping 20min, fully cleans with deionized water;
Step 102: the film that step 101 is obtained is transferred in the sulfonation acetophenone furfural condensation product solution of 8.0mg/mL, behind the dipping 20min, takes out, and uses washed with de-ionized water.
Repeat above-mentioned steps 7 times, can obtain described composite nanometer filtering film.
The prepared composite nanometer filtering film of embodiment 1-6 is under 0.6MPa pressure, to Ni
2+, Ca
2+Rejection and the flux of ion and dyestuff dimethyl phenol orange, rhodamine B are tested, and be as shown in table 1.
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Composite nanometer filtering film the separating of table 1 the present invention preparation to bivalent metal ion and dye solution
Claims (5)
1. composite nanometer filtering film based on aliphatic sulfonate condensation product preparation, comprise base membrane layer, composite film successively, described composite film is that cationic polyelectrolyte and anionic polyelectrolyte form through the static self assembly, it is characterized in that described anionic polyelectrolyte is an aliphatic sulfonate condensation product solution.
2. composite nanometer filtering film as claimed in claim 1 is characterized in that, described basement membrane is a molecular weight less than 100,000 milipore filter.
3. composite nanometer filtering film as claimed in claim 2 is characterized in that, described basement membrane is polyacrylonitrile ultrafiltration film, cellulose-acetafolic, polysulphone super-filter membrane, aluminium oxide ceramics milipore filter.
4. composite nanometer filtering film as claimed in claim 1 is characterized in that, described cationic polyelectrolyte comprises polymine PEI, poly-divinyl propyl ammonium chloride PDDA, polyvinylamine PVA.
5. composite nanometer filtering film as claimed in claim 1 is characterized in that, described anionic polyelectrolyte comprises sulfonated acetone formaldehyde condensation products, sulfonation cyclohexanone formaldehyde condensation products, sulfonation acetophenone furfural condensation product, sulfonation MEK formaldehyde condensation products.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449735A (en) * | 2013-08-26 | 2013-12-18 | 北京工业大学 | Nanometer calcium silicate hydrate super-hydrophilicity thin film as well as preparation method and applications of thin film |
| CN104028120A (en) * | 2014-05-16 | 2014-09-10 | 浙江大学 | Method for preparing carboxymethylcellulose sodium composite-filled polyamide nanofiltration membrane |
| CN104028119A (en) * | 2014-05-16 | 2014-09-10 | 浙江大学 | Preparation method of carboxylic acid betaine type complex modified polyamide nanofiltration membrane |
| CN106256839A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of method that ion blotting composite membrane is prepared in surface heat polymerization |
| CN106334447A (en) * | 2016-09-28 | 2017-01-18 | 东莞市联洲知识产权运营管理有限公司 | Anti-pollution composite nano filtering membrane for direct dye waste liquid treatment |
| CN107486026A (en) * | 2017-08-18 | 2017-12-19 | 清华大学 | Seperation film of stable against biological contamination and preparation method thereof |
| CN110787644A (en) * | 2019-10-15 | 2020-02-14 | 华中科技大学 | Loose nanofiltration membrane based on branched polyethyleneimine, and preparation and application thereof |
| CN111036097A (en) * | 2019-12-31 | 2020-04-21 | 宁波日新恒力科技有限公司 | Polyelectrolyte coating nanofiltration composite membrane for treating electroplating wastewater and application thereof |
| CN111423877A (en) * | 2020-03-12 | 2020-07-17 | 太原理工大学 | Sulfonated acetone-formaldehyde compound with ratio type pH fluorescence response and preparation method thereof |
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| CN1724128A (en) * | 2005-06-22 | 2006-01-25 | 南京工业大学 | Process for preparing organic and inorganic composite film by autoassembling tech |
| EP1832629A1 (en) * | 2006-03-10 | 2007-09-12 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449735A (en) * | 2013-08-26 | 2013-12-18 | 北京工业大学 | Nanometer calcium silicate hydrate super-hydrophilicity thin film as well as preparation method and applications of thin film |
| CN103449735B (en) * | 2013-08-26 | 2015-11-18 | 北京工业大学 | A kind of nanometer hydrated calcium silicate super-hydrophilic thin film and preparation method thereof and application |
| CN104028120A (en) * | 2014-05-16 | 2014-09-10 | 浙江大学 | Method for preparing carboxymethylcellulose sodium composite-filled polyamide nanofiltration membrane |
| CN104028119A (en) * | 2014-05-16 | 2014-09-10 | 浙江大学 | Preparation method of carboxylic acid betaine type complex modified polyamide nanofiltration membrane |
| CN104028119B (en) * | 2014-05-16 | 2015-12-02 | 浙江大学 | A kind of preparation method of carboxylic acid betaine type complex compound modified polyamide NF membrane |
| CN104028120B (en) * | 2014-05-16 | 2015-12-02 | 浙江大学 | Sodium carboxymethylcellulose compound fills the preparation method of polyamide nanofiltration membrane |
| CN106256839A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of method that ion blotting composite membrane is prepared in surface heat polymerization |
| CN106334447A (en) * | 2016-09-28 | 2017-01-18 | 东莞市联洲知识产权运营管理有限公司 | Anti-pollution composite nano filtering membrane for direct dye waste liquid treatment |
| CN107486026A (en) * | 2017-08-18 | 2017-12-19 | 清华大学 | Seperation film of stable against biological contamination and preparation method thereof |
| CN107486026B (en) * | 2017-08-18 | 2021-04-02 | 清华大学 | Separation membrane resistant to biological contamination and method for preparing same |
| CN110787644A (en) * | 2019-10-15 | 2020-02-14 | 华中科技大学 | Loose nanofiltration membrane based on branched polyethyleneimine, and preparation and application thereof |
| CN110787644B (en) * | 2019-10-15 | 2020-12-18 | 华中科技大学 | Loose nanofiltration membrane based on branched polyethyleneimine, and preparation and application thereof |
| CN111036097A (en) * | 2019-12-31 | 2020-04-21 | 宁波日新恒力科技有限公司 | Polyelectrolyte coating nanofiltration composite membrane for treating electroplating wastewater and application thereof |
| CN111036097B (en) * | 2019-12-31 | 2022-04-05 | 宁波日新恒力科技有限公司 | Polyelectrolyte coating nanofiltration composite membrane for treating electroplating wastewater and application thereof |
| CN111423877A (en) * | 2020-03-12 | 2020-07-17 | 太原理工大学 | Sulfonated acetone-formaldehyde compound with ratio type pH fluorescence response and preparation method thereof |
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| CN103223308B (en) | 2015-01-07 |
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