CN111359457A - Sulfonated polyarylethersulfone nanofiltration membrane and preparation method thereof - Google Patents
Sulfonated polyarylethersulfone nanofiltration membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 141
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 title claims abstract description 69
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000005266 casting Methods 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 239000011521 glass Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000007790 scraping Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000004907 flux Effects 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- PPCPANAWTNYWJR-UHFFFAOYSA-N 3-[2-fluoro-5-(4-fluoro-3-quinolin-3-ylphenyl)sulfonylphenyl]quinoline Chemical compound C1=CC=C2C(=C1)C=C(C=N2)C3=C(C=CC(=C3)S(=O)(=O)C4=CC(=C(C=C4)F)C5=CC6=CC=CC=C6N=C5)F PPCPANAWTNYWJR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 sulfonylbis (6-fluoro-3, 1-phenylene) Chemical class 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- FMHXJHFDKAXSKN-UHFFFAOYSA-N 2-bromo-4-(3-bromo-4-fluorophenyl)sulfonyl-1-fluorobenzene Chemical compound C1=C(Br)C(F)=CC=C1S(=O)(=O)C1=CC=C(F)C(Br)=C1 FMHXJHFDKAXSKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- YGDICLRMNDWZAK-UHFFFAOYSA-N quinolin-3-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CN=C21 YGDICLRMNDWZAK-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a preparation method of a sulfonated polyarylethersulfone nanofiltration membrane, belonging to the field of preparation of membrane separation materials.
Description
Technical Field
The invention belongs to the field of preparation of membrane separation materials, and particularly relates to a sulfonated polyarylethersulfone nanofiltration membrane and a preparation method thereof.
Background
The polyarylethersulfone material is a special engineering plastic which integrates the characteristics of easy molding and processing and high impact strength, has excellent dimensional stability, thermal stability, mechanical stability and good biocompatibility, and is widely applied to the fields of medicine, transportation, electronic and electric appliances and the like due to the advantages of excellent performance and low price. However, the hydrophobic nature of polyethersulfones limits their use and thus modification is required to increase hydrophilicity. The common modification method at present introduces sulfonic acid groups in a sulfonation mode, and the modified sulfonated polyether sulfone material has good hydrophilicity, acid and alkali resistance and chlorine resistance, and can be applied to the fields of fuel cell membranes, reverse osmosis membranes, ultrafiltration membranes and the like.
The sulfonated polyarylethersulfone membrane material has good mechanical property, chemical stability and thermal stability, low methanol permeability and low price, and the waste sulfonated polyarylethersulfone membrane is easy to degrade and does not pollute the environment, so the sulfonated polyarylethersulfone membrane material is expected to become a polyelectrolyte membrane material of a new generation. The invention provides a brand-new sulfonated polyarylethersulfone polymer, which has a simple preparation method and has great potential application value in the fields of fuel cell membranes, reverse osmosis membranes, ultrafiltration membranes and the like.
The nanofiltration membrane is a new field of membrane separation technology in recent years, has the characteristics of low operation pressure, energy conservation and the like, and is widely applied at present.
Disclosure of Invention
The invention provides a preparation method of a nanofiltration membrane, which is characterized by comprising the following steps:
step 1: adding sulfonated polyarylethersulfone into an organic solvent, heating to 50-100 ℃ under the condition of stirring, and dissolving until the sulfonated polyarylethersulfone is clear;
step 2: defoaming the solution obtained in the step 1;
and step 3: cooling the casting solution prepared in the step 2 to room temperature, pouring the casting solution on a glass plate or non-woven fabric, and scraping a nascent state membrane;
and 4, step 4: after the solvent in the nascent-state membrane is volatilized for 1-600 seconds, immersing the nascent-state membrane in deionized water at the temperature of 0-70 ℃ for solidification to form a membrane;
and 5: washing the membrane in the step 4 with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane,
wherein the sulfonated polyarylethersulfone has a structure as shown in formula (IA),
in some embodiments of the present invention, the organic solvent is selected from the group consisting of N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
In some embodiments of the present invention, the heating temperature in step 1 is 50-70 ℃.
In some embodiments of the present invention, the heating and stirring time in step 1 is 2 to 48 hours.
In some embodiments of the present invention, the heating and stirring time in step 1 is 12 to 36 hours.
In some schemes of the invention, the defoaming temperature is 30-60 ℃.
In some embodiments of the present invention, the defoaming temperature is 40 to 50 ℃.
In some schemes of the invention, the defoaming temperature is 35-45 ℃.
In some embodiments of the present invention, the defoaming time is 1 to 24 hours.
In some embodiments of the present invention, the defoaming time is 2 to 12 hours.
In some embodiments of the present invention, the defoaming time is 4 to 8 hours.
In some embodiments of the present invention, the volatilization time of the solvent in the nascent membrane is 60 to 200 seconds.
In some embodiments of the present invention, the volatilization time of the solvent in the nascent membrane is 60 to 150 seconds.
In some embodiments of the present invention, the volatilization time of the solvent in the nascent-state membrane is 60 to 120 seconds.
In some embodiments of the present invention, the volatilization time of the solvent in the nascent membrane is 90 to 120 seconds.
In some schemes of the invention, the nascent state membrane is immersed in deionized water at 30-60 ℃ for solidification to form the membrane.
In some schemes of the invention, the nascent state membrane is immersed in deionized water at 35-55 ℃ for solidification to form the membrane.
In some schemes of the invention, the nascent state membrane is immersed in deionized water at 40-50 ℃ for solidification to form the membrane.
In some schemes of the invention, the concentration of the sulfonated polyarylethersulfone in the membrane casting solution is 20-40 wt%.
In some schemes of the invention, the concentration of the sulfonated polyarylethersulfone in the membrane casting solution is 25-35 wt%.
In some schemes of the invention, the concentration of the sulfonated polyarylethersulfone in the membrane casting solution is 28-32 wt%.
In some embodiments of the present invention, the thickness of the nascent membrane is 50 to 300 μm.
In some embodiments of the present invention, the thickness of the nascent membrane is 100 to 300 μm.
The invention has the beneficial effects that:
the invention provides a chemical polyarylethersulfone nanofiltration membrane with a brand new structure, which is simple in preparation method, has excellent water flux and separation performance, and has great potential industrial application value.
Detailed Description
The following detailed description of specific embodiments of the present invention is provided to illustrate and explain the present invention and to be understood not to limit the present invention.
Example 1: synthesis of sulfonated Polyarylethersulfone (IA)
Step 1: synthesis of 3,3' - (sulfonylbis (6-fluoro-3, 1-phenylene)) bisquinoline (I-c)
4,4' -sulfonylbis (2-bromo-1-fluorobenzene) (8.24g, 20mmol) was dissolved in 100mL of tetrahydrofuran, 0.2g of tetrakis (triphenylphosphine) palladium was added, quinoline-3-boronic acid (7.26g, 42mmol) was added, and the mixture was heated under reflux for 12 hours under nitrogen protection. After the reaction was completed, 100mL of water was added thereto, and the mixture was stirred for 1 hour and filtered to obtain a crude product of 3,3'- (sulfonylbis (6-fluoro-3, 1-phenylene)) biquinoline, which was recrystallized from toluene to obtain 8.63g of a crude product of 3,3' - (sulfonylbis (6-fluoro-3, 1-phenylene)) biquinoline in a yield of 85%.
MS m/z：509.2[M+H]+
Step 2: synthesis of polyarylethersulfone (I-e)
3,3'- (sulfonylbis (6-fluoro-3, 1-phenylene)) bisquinoline (5.08g, 10mmol), 4' - (1, 3-dioxolan-2, 2-diyl) diphenol (2.89g, 11.5mmol), anhydrous potassium carbonate (1.59g, 11.5mmol), N-methylpyrrolidone (40mL) and toluene (10mL) were charged into a reaction flask, and reacted under reflux for 10 hours while the water separator removed the water in the system. Evaporating toluene in the system, continuing to react for 7 hours at 160 ℃, after the reaction is finished, slowly dropwise adding absolute ethyl alcohol (200mL) into the reaction liquid within 3 hours, stirring to separate out a large amount of white solid, continuing to stir for 1 hour, and filtering to obtain polyarylether sulfone (I-e) (6.47g, yield 83%).
And step 3: preparation of sulfonated polyarylethersulfones (Ia)
Dissolving polyarylethersulfone (I-e) (3.6g, 5mmol) in concentrated sulfuric acid (100mL), heating to 45 ℃, stirring for 5 hours, after the reaction is finished, slowly dripping the reaction liquid into 2L of ice water under the condition of vigorous stirring, continuing stirring for 1 hour after dripping is finished, and filtering to obtain sulfonated polyarylethersulfone (IA).
Example 2: preparation of sulfonated polyarylethersulfone nanofiltration membrane 1
Adding sulfonated polyarylethersulfone (IA) (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the condition of stirring, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing for 12 hours at 60 ℃ for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 60 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at the temperature of 40 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 1.
Example 3: preparation of sulfonated polyarylethersulfone nanofiltration membrane 2
Adding sulfonated polyarylethersulfone (IA) (2.8g) into N-methylpyrrolidone (7.2g), heating to 60 ℃ under the condition of stirring, completely dissolving the sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing at 60 ℃ for 12 hours for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 60 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at the temperature of 40 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 2.
Example 4: preparation of sulfonated polyarylethersulfone nanofiltration membrane 3
Adding sulfonated polyarylethersulfone (IA) (3.2g) into N-methylpyrrolidone (6.8g), heating to 60 ℃ under the condition of stirring, completely dissolving the sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing at 60 ℃ for 12 hours for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 60 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at the temperature of 40 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 3.
Example 5: preparation of sulfonated poly (aryl ether sulfone) nanofiltration membrane 4
Adding sulfonated polyarylethersulfone (IA) (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the condition of stirring, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing for 12 hours at 60 ℃ for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 60 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at the temperature of 30 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 4.
Example 6: preparation of sulfonated polyarylethersulfone nanofiltration membrane 5
Adding sulfonated polyarylethersulfone (IA) (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the condition of stirring, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing for 12 hours at 60 ℃ for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 60 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at 50 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 5.
Example 7: preparation of sulfonated polyarylethersulfone nanofiltration membrane 6
Adding sulfonated polyarylethersulfone (IA) (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the condition of stirring, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing for 12 hours at 60 ℃ for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 40 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at the temperature of 50 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 6.
Example 8: preparation of sulfonated poly (aryl ether sulfone) nanofiltration membrane 7
Adding sulfonated polyarylethersulfone (IA) (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the condition of stirring, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing for 12 hours at 60 ℃ for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 90 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at 50 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 7.
Example 9: preparation of control nanofiltration membranes
Adding Nafion (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the stirring condition, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing at 60 ℃ for 12 hours for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 90 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at 50 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain a control nanofiltration membrane.
Experimental example 1: water absorption test
Homogeneous sulfonated poly (aryl ether sulfone) (I-B) and Nafion membrane are soaked in deionized water for 24h under the test conditions of 25 ℃ and 80 ℃, and then the mass Mw of the soaked homogeneous membrane is weighed by an analytical balance. And (3) putting the soaked sample into a vacuum drying oven, drying for 24 hours at 75 ℃, weighing the mass Md of the dry film after the sample is completely dried, and calculating the water absorption rate according to the formula of (Mw-Md)/Md x 100%. The results of the experiment are shown in table 1.
Experimental example 2: measurement of ion exchange Capacity
Weighing fully dried sulfonated polyarylethersulfone (I-B) and a Nafion blank membrane (weight is recorded as M), dissolving the sulfonated polyarylethersulfone (I-B) and the Nafion blank membrane by using N-methylpyrrolidone as a solvent and 10 mLN-methylpyrrolidone, adding 10mL of deionized water after fully dissolving, using methyl red as an indicator, titrating by using a calibrated NaOH solution (concentration is recorded as C1) (the volume consumed by NaOH is recorded as V1), testing for 3 times, and calculating the ion exchange capacity by using a formula (2), wherein the formula is IEC (V1) and C1/M. The results of the experiment are shown in table 1.
TABLE 1
Experimental example 3: nanofiltration test experiment
The experiment adopts a cross-flow filtration method: under the conditions of 25 ℃ of temperature, 0.6MPa of pressure and 18.1cm of effective area 2, 2g/L magnesium sulfate solution is adopted as test feed liquid, the membrane is pre-pressed to ensure that the permeability of the membrane is stable, then flux and interception are measured once every 5 minutes, and the average value is taken as the final test result after 3 times of tests. The membrane flux J is calculated as J ═ V/(A ×) and V is the volume of the permeation flux, A is the area of the effective membrane and t is the time; the retention rate R is calculated by the formula of R ═ 1-Cp/Cf)*100％，CpAs the concentration of the feed solution, CfIs the permeate concentration.
The test results of the sulfonated polyarylethersulfone nanofiltration membranes 1-7 and the control nanofiltration membrane are shown in table 2.
TABLE 2
| Test sample | Flow rate (L/(m)2*h)) | Retention (%) |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 1 | 51.3 | 79.8 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 2 | 51.1 | 78.7 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 3 | 49.8 | 81.2 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 4 | 54.6 | 73.8 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 5 | 50.5 | 80.3 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 6 | 51.0 | 79.1 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 7 | 50.6 | 78.8 |
| Control nanofiltration membranes | 43.7 | 76.5 |
The results show that the sulfonated polyarylethersulfone nanofiltration membrane has higher water flux, higher retention rate and excellent separation effect.
Claims (8)
1. The preparation method of the nanofiltration membrane is characterized by comprising the following steps:
step 1: adding sulfonated polyarylethersulfone into an organic solvent, heating to 50-100 ℃ under the condition of stirring, and dissolving until the sulfonated polyarylethersulfone is clear;
step 2: defoaming the solution obtained in the step 1;
and step 3: cooling the casting solution prepared in the step 2 to room temperature, pouring the casting solution on a glass plate or non-woven fabric, and scraping a nascent state membrane;
and 4, step 4: after the solvent in the nascent-state membrane is volatilized for 1-600 seconds, immersing the nascent-state membrane in deionized water at the temperature of 0-70 ℃ for solidification to form a membrane;
and 5: washing the membrane in the step 4 with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane,
wherein the sulfonated polyarylethersulfone has a structure as shown in formula (IA),
2. nanofiltration membrane preparation method according to claim 1, wherein the organic solvent is selected from the group consisting of N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
3. The nanofiltration membrane preparation method according to claim 1, wherein the deaeration temperature is 30-60 ℃.
4. The nanofiltration membrane preparation method according to claim 1, wherein the defoaming time is 1-24 hours.
5. The nanofiltration membrane preparation method according to claim 1, wherein the volatilization time of the solvent in the nascent membrane is 60-200 seconds.
6. The nanofiltration membrane preparation method according to claim 1, wherein the nascent membrane is immersed in deionized water at 30-60 ℃ to be solidified into a membrane.
7. The nanofiltration membrane preparation method according to claim 1, wherein the concentration of the sulfonated polyarylethersulfone in the membrane casting solution is 20-40 wt%.
8. The nanofiltration membrane preparation method according to claim 1, wherein the thickness of the nascent membrane is 50-300 μm.
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