CN106178993B - A kind of supermolecule polymer nanofiltration membrane and preparation method thereof - Google Patents
A kind of supermolecule polymer nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN106178993B CN106178993B CN201610708212.4A CN201610708212A CN106178993B CN 106178993 B CN106178993 B CN 106178993B CN 201610708212 A CN201610708212 A CN 201610708212A CN 106178993 B CN106178993 B CN 106178993B
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- 239000012528 membrane Substances 0.000 title claims abstract description 84
- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 40
- 125000002091 cationic group Chemical group 0.000 claims abstract description 32
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 210000004379 membrane Anatomy 0.000 claims abstract description 16
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 11
- 238000001338 self-assembly Methods 0.000 claims abstract description 10
- 230000005611 electricity Effects 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 56
- 238000004140 cleaning Methods 0.000 claims description 44
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 230000002209 hydrophobic effect Effects 0.000 claims description 23
- 230000002000 scavenging effect Effects 0.000 claims description 23
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 14
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 7
- 229910001447 ferric ion Inorganic materials 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- -1 Co2 + Chemical compound 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000003068 static effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- 239000011780 sodium chloride Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000007832 Na2SO4 Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000007757 hot melt coating Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Chemical class 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Chemical class [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of supermolecule polymer nanofiltration membranes and preparation method thereof.The nanofiltration membrane is assembling object with supermolecule polymer, covalent type cationic polyelectrolyte using ultrafiltration membrane as basement membrane, is prepared using the method for dynamic and static mixing LBL self-assembly, wherein ultrafiltration membrane bear electricity, molecular cut off is less than 70,000；Supermolecule polymer is corrdination type supermolecule polymer.It is convenient to adjust the structure of nanofiltration membrane by adjusting the proportion of transition metal ions type, metal ion and ligand, concentration, the concentration of supermolecule polymer, the type of covalent type cationic polyelectrolyte, the assembling number of plies, type of basement membrane etc., the nanofiltration membrane for adapting to different demands is prepared, entire assembling process solvent for use is water, and preparation process is environmentally protective.
Description
Technical field
The invention belongs to Nanofiltration-membrane technique fields, and in particular to a kind of supermolecule polymer nanofiltration membrane and preparation method thereof.
Background technique
Nanofiltration membrane is that a kind of membrane aperture is less than 2nm using pressure as the novel separation film of driving force.Alternative separation monovalence,
Divalent ion is high to small organic molecule rejection.The fields such as food, medicine, chemical industry are currently widely used for, especially in hard water
Softening obtains people with harmful ion removal etc. in water and greatly pays close attention to.For high-quality nanofiltration membrane, high-throughput, selectivity
Good, antipollution, performance stabilization, energy-saving and environmental protection are its notable features.To achieve the purpose that high-throughput, selectivity is good, people are often
Composite membrane is prepared, i.e., covers one layer of very thin selective separation layer in the biggish membrane surface of the preferable flux of intensity, method has painting
It covers, interfacial polymerization, surface grafting polymerization etc..Studies have shown that polyelectrolyte membrane surface LBL self-assembly can be obtained it is very thin (≤
Selective separation layer 50nm), and by adjust assembling condition can control membrane flux and selectivity etc. performances, nanofiltration membrane at
One of membrane process can be completed in aqueous solution, environmentally protective, therefore become research hotspot.From charge density of polyelectrolyte, assembling
The swellability of outermost layer polyelectrolyte composition, film is to factors such as feeding liquid concentration, operating pressures to nano filter membrane separating property afterwards
Careful detailed research has been carried out in influence.Packaging efficiency is also under the action of introducing outfield (electric-field enhancing, pressure-driven etc.)
Be greatly improved, but substance used in the preparation nanofiltration membrane of self assembly at present be mostly with the polyelectrolyte of Covalent bonding together,
In recent years, graphene oxide, silver etc. are also introduced into interlayer by someone.But it is assembled using the supermolecule polymer that non-covalent bond combines
The research of nanofiltration membrane has not been reported.
Supermolecule polymer is put forward for the first time in nineteen ninety by French scientist Lehn, be monomeric unit with it is reversible, highly take
To the polymer that is combined into of non-covalent interaction.It can not only form highly viscous weak solution, obtain similar tradition
The rheological characteristic of polymer, simultaneously because it is combined with weak secondary interaction, structure and performance can be with the changes of environmental stimuli
Change and changes.Have many characteristics, such as easy processing, selfreparing, stimuli responsive.Therefore, people attempt to be applied to medicine controlled releasing, divide
Son identification, selfreparing high molecular material such as hot melt coating etc., but correlative study is had no for separation membrane.
Summary of the invention
The object of the present invention is to provide a kind of supermolecule polymer nanofiltration membranes and preparation method thereof, using supermolecule polymer
Building nanofiltration membrane is not only that nanofiltration membrane provides new substance selection, has opened up new purposes, Er Qieyu for supermolecule polymer
Conventional polyelectrolyte self assembly is compared, and the control measures of membrane structure increase, and can regulate and control through a variety of ways membrane structure to be fitted
Nanofiltration membrane, and the assembling number of plies is few, it is high-efficient, it is suitble to actual production.
The present invention is realized by following technical proposals.
A kind of supermolecule polymer nanofiltration membrane, using the polyacrylonitrile ultrafiltration film of alkali modification or sulfonated polyether sulfone ultrafiltration membrane as base
Film is prepared by supermolecule polymer and covalent type cationic polyelectrolyte LBL self-assembly.Ultrafiltration membrane used in it
Molecular cut off is less than 70,000, and supermolecule polymer is coordinated with double blank oxalate ligand in the wrong by transition metal ions and is formed, covalent type sun
Cationic polyelectrolyte includes polyethyleneimine, polyvinylamine, poly diallyldimethylammonium chloride, poly- N, N- dimethyl diallyl chlorination
Ammonium, chitosan etc..
A kind of preparation method of supermolecule polymer nanofiltration membrane first under pressurised conditions impregnates the ultrafiltration membrane of charge
In covalent type cationic polyelectrolyte solution, so that in conjunction with ultrafiltration membrane, it is compound to obtain polycation for cationic polyelectrolyte
Polycation composite membrane, is then immersed in supermolecule polymer solution by film, deionized water cleaning, supermolecule polymer and poly-
The cationic polyelectrolyte of cationic composite film surface combines, deionized water cleaning, repeatedly, the layer needed for obtaining
Number, obtains supermolecule polymer nanofiltration membrane.
Specific step is as follows:
1) preparing mass percent concentration is 0.1%-0.5% covalent type cationic polyelectrolyte solution, and inorganic salts are added,
Inorganic salt concentration is 0.1M-2M, and adjusting pH value is 2.5-3.5.
2) a certain concentration transition metal ion solution is prepared respectively and double blank bends oxalic acid solution, adjust pH value with buffer solution
For 5.4-6.5, the concentration of two kinds of solution is 1mmol/L-5mmol/L, then according to a certain ratio mixes two kinds of solution, puts
It sets, it is to be assembled.
3) by after alkali modification polyacrylonitrile ultrafiltration film or sulfonated polyether sulfone ultrafiltration membrane be fixed on one band porous support layer
Container in, upward, covalent type cationic polyelectrolyte solution, pressurization, the poly- electrolysis of cation is then added in film surface into container
Matter passes through electrostatic force, hydrogen bond, hydrophobic force etc. in conjunction with basement membrane, built-up time 1-35min.
4) use deionized water cleaning step 3) gained film surface, scavenging period 1-10min.
5) toward cleaning after film surface be added supermolecule polymer solution, by electrostatic force, hydrogen bond, hydrophobic force etc. with
Cationic polyelectrolyte combines, built-up time 10-60min.
6) deionized water cleaning step 5 is used) surface of gained film, scavenging period 1-10min is placed at 90 degree of baking oven heat
1-3min is managed, it is double-deck to obtain first assembling.
7) cationic polyelectrolyte, pressurization, by electrostatic force, hydrogen bond, hydrophobic force is added toward the film surface after cleaning
Deng in conjunction with supermolecule polymer, built-up time 1-35min.
8) use deionized water cleaning step 7) gained film surface, scavenging period 1-10min.
9) toward cleaning after film surface be added supermolecule polymer solution, by electrostatic force, hydrogen bond, hydrophobic force etc. with
Cationic polyelectrolyte combines, built-up time 10-60min.
10) use deionized water cleaning step 9) gained film surface, scavenging period 1-10min.
Repeat step 7) -10) repeatedly to the required double-deck number, obtain nanofiltration membrane.
The molar ratio that transition metal ions of the present invention and double blank bend oxalate ligand is 3: 1-1: 3.The transition metal
Ion is Zn2+, Cu2+, Co2+, Fe2+, Fe3+, Eu3+、La3+In any one.
The invention has the benefit that using supermolecule polymer building nanofiltration membrane be only nanofiltration membrane provide it is new
Substance selection, and the control measures of membrane structure increase compared with conventional polyelectrolyte self assembly, applicable transition metal ions
And polycation electrolyte type is more, entire assembling process solvent for use is water, and preparation process is environmentally protective, and dynamic and static
Assembling combines, and the assembling number of plies is few, high-efficient, is suitble to actual production.
Specific embodiment
The present invention is using charged ultrafiltration membrane as basement membrane, with corrdination type supermolecule polymer and covalent type cationic polyelectrolyte
To assemble substance, nanofiltration membrane is prepared using the LBL self-assembly method of dynamic and static combination.By adjusting transition metal ions kind
Class, the proportion of metal ion and ligand, concentration, the concentration of supermolecule polymer, the type of covalent type polyelectrolyte, assembled layers
Number, type of basement membrane etc. are convenient to adjust the structure of nanofiltration membrane, and the nanofiltration membrane for adapting to different demands is prepared.
Wherein, charged ultrafiltration membrane is the polyacrylonitrile film or sulfonated polyether sulfone ultrafiltration membrane of alkali modification, and molecular cut off is less than 7
Ten thousand.
The supermolecule polymer used in the present invention bends oxalate ligand and passes through coordination bond for transition metal ions and double blank
It closes, applicable transition metal ions has Zn2+, Cu2+, Co2+, Fe2+, Fe3+, Eu3+And La3+Deng.
The covalent type cationic polyelectrolyte being applicable in the present invention has polyethyleneimine, polyvinylamine, polyallyl chlorination
Ammonium, poly- N, N- dimethyl diallyl ammonium chloride, chitosan etc..
The dynamic and static self-assembling method used in the present invention is respectively to pressurize and be not pressurized under effect, assembles molecule and base
Between film, between assembling molecule electrostatic interaction, hydrophobic force, the hydrogen bond the effects of under the package technique that combines, wherein dynamic self-assembly
External pressure size used is 0.01MPa-0.8MPa.
The separating property of nanofiltration membrane prepared by the present invention is using cross-current type film evaluation instrument and conductivity meter test.Test temperature
For room temperature, test pressure is 0.6MPa.Permeability of the membrane is characterized (single with the water flux of film under this condition or salting liquid flux
Position: L/m2.h)；The selective penetrated property of film is with film respectively to the NaCl of 1000mg/L, MgCl2, Na2SO4And MgSO4Salt in solution
Removal efficiency characterizes.
Embodiment 1:
Ultrafiltration membrane used in the present embodiment is the polyacrylonitrile ultrafiltration film alkali modification product that molecular cut off is 50,000.Supermolecule
Polymer is by Zn2+Ion and double blank bend oxalate ligand coordination gained.
Assembling is carried out in the porcelain container with open support that a diameter is 10cm.By the film surface court of ultrafiltration membrane
On, edge is fixed, and it places in a reservoir, is assembled according to the following steps:
1) preparing mass percent concentration is 0.2% poly diallyldimethylammonium chloride solution, and NaCl is added, and NaCl concentration is
0.5M, adjusting pH value is 2.5.
2) 5mmol/L zinc ion solution is prepared respectively and double blank bends oxalic acid solution, adjusting pH value with buffer solution is 5.4,
By Zn2+∶L2EO4=1: 1 ratio mixes two kinds of solution, and supermolecule polymer is obtained after placement, to be assembled.
3) poly diallyldimethylammonium chloride solution is added into container, pressurize 0.1MPa, by electrostatic force, hydrogen bond, hydrophobic
Power etc. is in conjunction with basement membrane, built-up time 5min.
4) use deionized water cleaning step 3) gained film surface, scavenging period 1min.
5) toward cleaning after film surface be added supermolecule polymer solution, by electrostatic force, hydrogen bond, hydrophobic force etc. with
Cationic polyelectrolyte combines, built-up time 30min.
6) deionized water cleaning step 5 is used) surface of gained film, scavenging period 1min is placed in the heat treatment of 90 degree of baking ovens
It is double-deck to obtain first assembling by 1.5min.
7) poly diallyldimethylammonium chloride solution is added toward the film surface after cleaning, pressurize 0.1MPa, by electrostatic force, hydrogen
Key, hydrophobic force etc. are in conjunction with supermolecule polymer, built-up time 5min.
8) use deionized water cleaning step 7) gained film surface, scavenging period 1min.
9) toward cleaning after film surface be added supermolecule polymer solution, by electrostatic force, hydrogen bond, hydrophobic force etc. with
Cationic polyelectrolyte combines, built-up time 30min.
10) use deionized water cleaning step 9) gained film film surface, scavenging period 1min.
The nanofiltration membrane that wheel number is 2 wheels must be assembled, the separating property of nanofiltration membrane obtained by the embodiment is see table 1.
Embodiment 2
Ultrafiltration membrane used in the present embodiment is the poly (ether-sulfone) ultrafiltration membrane that molecular cut off is 30,000.Supermolecule polymer is by Fe3+From
Son bends oxalate ligand coordination gained with double blank.
Assembling is carried out in the porcelain container with open support that a diameter is 10cm.By the film surface court of ultrafiltration membrane
On, edge is fixed, and it places in a reservoir, is assembled according to the following steps:
1) preparing mass percent concentration is 0.3% poly diallyldimethylammonium chloride solution, and NaCl is added, and NaCl concentration is
0.5M, adjusting pH value is 3.0.
2) 5mmol/L ferric ion solutions are prepared respectively and double blank bends oxalic acid solution, adjusting pH value with buffer solution is 5.4,
By Fe3+∶L2EO4=1: 2 ratio mixes two kinds of solution, and supermolecule polymer is obtained after placement.
3) poly diallyldimethylammonium chloride solution is added into container, pressurize 0.1MPa, by electrostatic force, hydrogen bond, hydrophobic
Power etc. is in conjunction with basement membrane, built-up time 10min.
4) use deionized water cleaning step 3) gained film surface, scavenging period 5min.
5) toward cleaning after film surface be added supermolecule polymer solution, by electrostatic force, hydrogen bond, hydrophobic force etc. with
Cationic polyelectrolyte combines, built-up time 30min.
6) deionized water cleaning step 5 is used) surface of gained film, scavenging period 5min is placed in the heat treatment of 90 degree of baking ovens
It is double-deck to obtain first assembling by 2min.
7) poly diallyldimethylammonium chloride solution is added toward the film surface after cleaning, pressurize 0.1MPa, by electrostatic force, hydrogen
Key, hydrophobic force etc. are in conjunction with supermolecule polymer, built-up time 10min.
8) use deionized water cleaning step 7) gained film surface, scavenging period 5min.
9) toward cleaning after film surface be added supermolecule polymer solution, by electrostatic force, hydrogen bond, hydrophobic force etc. with
Cationic polyelectrolyte combines, built-up time 30min.
10) use deionized water cleaning step 9) gained film surface, scavenging period 5min.
The nanofiltration membrane that wheel number is 2 wheels must be assembled, the separating property of nanofiltration membrane obtained by the embodiment is see table 1.
Embodiment 3
By the condition of example 1, by Zn2+∶L2EO4=1: 2 ratio coordination prepares supermolecule polymer, obtains after assembling two-wheeled
Nanofiltration membrane, the separating property of 3 film of example is see table 1.
Embodiment 4
Ultrafiltration membrane used in the present embodiment is the polyacrylonitrile ultrafiltration film alkali modification product that molecular cut off is 50,000.Supermolecule
Polymer is by Zn2+Ion and double blank bend oxalate ligand coordination gained.
Assembling is carried out in the porcelain container with open support that a diameter is 10cm.By the film surface court of ultrafiltration membrane
On, edge is fixed, and it places in a reservoir, is assembled according to the following steps:
1) preparing mass percent concentration is 0.2% poly diallyldimethylammonium chloride solution, and NaCl is added, and NaCl concentration is
0.5M, adjusting pH value is 2.5.
2) 5mmol/L zinc ion solution is prepared respectively and double blank bends oxalic acid solution, adjusting pH value with buffer solution is 5.4,
By Zn2+∶L2EO4=1: 2 ratio mixes two kinds of solution, after placing a period of time, obtains supermolecule polymer and carries out self assembly.
3) poly diallyldimethylammonium chloride solution is added into container, pressurize 0.1MPa, by electrostatic force, hydrogen bond, hydrophobic
Power etc. is in conjunction with basement membrane, built-up time 5min.
4) use deionized water cleaning step 3) gained film surface, scavenging period 1min.
5) toward cleaning after film surface be added supermolecule polymer solution, by electrostatic force, hydrogen bond, hydrophobic force etc. with
Cationic polyelectrolyte combines, built-up time 30min.
6) deionized water cleaning step 5 is used) surface of gained film, scavenging period 1min is placed in the heat treatment of 90 degree of baking ovens
1.5min.It is double-deck to obtain first assembling.
7) poly diallyldimethylammonium chloride solution is added toward the film surface after cleaning, pressurize 0.1MPa, by electrostatic force, hydrogen
Key etc. is in conjunction with supermolecule polymer, built-up time 5min.
8) use deionized water cleaning step 7) gained film surface, scavenging period 1min.
The nanofiltration membrane that wheel number is 1.5 wheels must be assembled, the separating property of nanofiltration membrane obtained by the embodiment is see table 1.
Embodiment 5
By the condition of embodiment 3, step 7) -10 is repeated) once, repeat step 7) -8) primary must assemble that take turns number be 3.5
The nanofiltration membrane of wheel, the separating property of embodiment gained nanofiltration membrane is see table 1.
Embodiment 6
Ultrafiltration membrane used in the present embodiment is the polyacrylonitrile ultrafiltration film alkali modification product that molecular cut off is 50,000.Supermolecule
Polymer is by Zn2+Ion and double blank bend oxalate ligand coordination gained.
Assembling is carried out in the porcelain container with open support that a diameter is 10cm.By the film surface court of ultrafiltration membrane
On, edge is fixed, and it places in a reservoir, is assembled according to the following steps:
1) preparing mass percent concentration is 0.5% poly diallyldimethylammonium chloride solution, and NaCl is added, and NaCl concentration is
0.5M, adjusting pH value is 2.5.
2) 1mmol/L zinc ion solution is prepared respectively and double blank bends oxalic acid solution, adjusting pH value with buffer solution is 5.4,
By Zn2+∶L2EO4=1: 1 ratio mixes two kinds of solution, and supermolecule polymer is obtained after placement, to be assembled.
3) poly diallyldimethylammonium chloride solution is added into container, pressurize 0.1MPa, by electrostatic force, hydrogen bond, hydrophobic
Power etc. is in conjunction with basement membrane, built-up time 5min.
4) use deionized water cleaning step 3) gained film surface, scavenging period 1min.
5) toward cleaning after film surface be added supermolecule polymer solution, by electrostatic force, hydrogen bond, hydrophobic force etc. with
Cationic polyelectrolyte combines, built-up time 30min.
6) deionized water cleaning step 5 is used) surface of gained film, scavenging period 1min is placed in the heat treatment of 90 degree of baking ovens
It is double-deck to obtain first assembling by 1.5min.
7) poly diallyldimethylammonium chloride solution is added toward the film surface after cleaning, pressurize 0.1MPa, by electrostatic force, hydrogen
Key, hydrophobic force etc. are in conjunction with supermolecule polymer, built-up time 5min.
8) use deionized water cleaning step 7) gained film surface, scavenging period 1min.
9) toward cleaning after film surface be added supermolecule polymer solution, by electrostatic force, hydrogen bond, hydrophobic force etc. with
Cationic polyelectrolyte combines, built-up time 30min.
10) use deionized water cleaning step 9) gained film film surface, scavenging period 1min.
The nanofiltration membrane that wheel number is 2 wheels must be assembled, the separating property of nanofiltration membrane obtained by the embodiment is see table 1.
The separating property of gained nanofiltration membrane in 1 embodiment of table
Claims (3)
1. a kind of supermolecule polymer nanofiltration membrane, it is characterised in that using ultrafiltration membrane as basement membrane, pass through supermolecule polymer and poly- electricity
Solution matter is obtained in its surface alternating layers self assembly；The ultrafiltration membrane is that alkali modification polyacrylonitrile ultrafiltration film or sulfonated polyether sulfone are super
Filter membrane, molecular cut off is less than 70,000；The supermolecule polymer be corrdination type supermolecule polymer, by transition metal ions with
Double blank is bent oxalate ligand coordination and is made, and transition metal ion solution and double blank bend the concentration of oxalic acid solution as 1mmol/L-5mmol/
The molar ratio that L, transition metal ions and double blank bend oxalate ligand is 3:1-1:3, and the transition metal ions is Zn2+, Cu2+, Co2 +, Fe2+, Fe3+, Eu3+、La3+In any one；The polyelectrolyte is covalent type cationic polyelectrolyte；The covalent type
Cationic polyelectrolyte is polyethyleneimine, polyvinylamine, poly diallyldimethylammonium chloride, poly- N, N- dimethyl diallyl ammonium chloride
Or chitosan.
2. a kind of preparation method of supermolecule polymer nanofiltration membrane, it is characterised in that: first under pressurised conditions by charge
Ultrafiltration membrane is immersed in covalent type cationic polyelectrolyte solution, so that cationic polyelectrolyte in conjunction with ultrafiltration membrane, is gathered
Polycation composite membrane, is then immersed in supermolecule polymer solution, supermolecule by cationic composite membrane, deionized water cleaning
Polymer is in conjunction with the cationic polyelectrolyte of polycation composite film surface, deionized water cleaning, repeatedly, until obtaining
The required number of plies obtains supermolecule polymer nanofiltration membrane；
Specific step is as follows:
1) preparing mass percent concentration is 0.1%-0.5% covalent type cationic polyelectrolyte solution, and inorganic salts are added, inorganic
Salinity is 0.1M-2M, and adjusting pH value is 2.5-3.5；
2) transition metal ion solution and double blank are prepared respectively bend oxalic acid solution, adjusting pH value with buffer solution is 5.4-6.5, two
The concentration of kind solution is 1mmol/L-5mmol/L, is then according to the molar ratio that transition metal ions and double blank bend oxalate ligand
3:1-1:3 mixes two kinds of solution, places, to be assembled；
3) by after alkali modification polyacrylonitrile ultrafiltration film or sulfonated polyether sulfone ultrafiltration membrane be fixed on the appearance with porous support layer
In device, upward, covalent type cationic polyelectrolyte solution, pressurization is then added in film surface into container, and cationic polyelectrolyte leads to
Electrostatic force, hydrogen bond, hydrophobic force are crossed in conjunction with basement membrane, built-up time 1-35min；
4) use deionized water cleaning step 3) gained film surface, scavenging period 1-10min；
5) supermolecule polymer solution is added toward the film surface after cleaning, by electrostatic force, hydrogen bond, hydrophobic force and cation
Polyelectrolyte combines, built-up time 10-60min；
6) deionized water cleaning step 5 is used) surface of gained film, scavenging period 1-10min is placed in 90 degree of baking ovens heat treatment 1-
It is double-deck to obtain first assembling by 3min；
7) cationic polyelectrolyte is added toward the film surface after cleaning, pressurization by electrostatic force, hydrogen bond, hydrophobic force and surpasses
Molecularly Imprinted Polymer combines, built-up time 1-35min；
8) use deionized water cleaning step 7) gained film surface, scavenging period 1-10min；
9) supermolecule polymer solution is added toward the film surface after cleaning, by electrostatic force, hydrogen bond, hydrophobic force and cation
Polyelectrolyte combines, built-up time 10-60min；
10) use deionized water cleaning step 9) gained film surface, scavenging period 1-10min；
Repeat step 7) -10) repeatedly to the required double-deck number, obtain nanofiltration membrane.
3. the preparation method of supermolecule polymer nanofiltration membrane according to claim 2, it is characterised in that: the transition metal from
Son is Zn2+, Cu2+, Co2+, Fe2+, Fe3+, Eu3+、La3+In any one.
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