CN115301086B - Perfluorinated polymer-based composite nanofiltration membrane - Google Patents
Perfluorinated polymer-based composite nanofiltration membrane Download PDFInfo
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- CN115301086B CN115301086B CN202210946868.5A CN202210946868A CN115301086B CN 115301086 B CN115301086 B CN 115301086B CN 202210946868 A CN202210946868 A CN 202210946868A CN 115301086 B CN115301086 B CN 115301086B
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- 239000012528 membrane Substances 0.000 title claims abstract description 157
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 229920000642 polymer Polymers 0.000 title claims abstract description 25
- 238000009987 spinning Methods 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000004642 Polyimide Substances 0.000 claims abstract description 14
- 229920001721 polyimide Polymers 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 65
- 229920005548 perfluoropolymer Polymers 0.000 claims description 49
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 30
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000012071 phase Substances 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 19
- 239000002121 nanofiber Substances 0.000 claims description 19
- -1 polypropylene Polymers 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 14
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 13
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 13
- 239000008346 aqueous phase Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 10
- 108010010803 Gelatin Proteins 0.000 claims description 9
- 229920000159 gelatin Polymers 0.000 claims description 9
- 239000008273 gelatin Substances 0.000 claims description 9
- 235000019322 gelatine Nutrition 0.000 claims description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229920003169 water-soluble polymer Polymers 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 238000012695 Interfacial polymerization Methods 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000012510 hollow fiber Substances 0.000 claims description 5
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 3
- 238000010382 chemical cross-linking Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- 229920005575 poly(amic acid) Polymers 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 229920005594 polymer fiber Polymers 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 47
- 239000004372 Polyvinyl alcohol Substances 0.000 description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 description 19
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 19
- 230000004907 flux Effects 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229930187593 rose bengal Natural products 0.000 description 4
- 229940081623 rose bengal Drugs 0.000 description 4
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 229920001108 Polyimide P84 Polymers 0.000 description 3
- 240000008254 Rosa chinensis Species 0.000 description 3
- 235000000664 Rosa chinensis Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003849 solvent resist ant nanofiltration Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- 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
-
- 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
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
- B01D69/088—Co-extrusion; Co-spinning
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/50—Control of the membrane preparation process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/40—Fibre reinforced membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a perfluorinated polymer-based composite nanofiltration membrane. According to the invention, the perfluorinated polymer is used as a base film material, and the electrostatic spinning co-spinning polyimide and the perfluorinated polymer fiber are interwoven to provide a rigid support, so that the problems that the perfluorinated polymer film is difficult to modify, serious in shrinkage in a sintering process and uncontrollable in structure are solved. The co-spinning polyimide provides a reactive site on the surface of the membrane, a stable cross-linking structure between the base membrane and the separation layer is constructed, the interface bonding strength of the base membrane and the separation layer is obviously improved, and the service life of the membrane is effectively prolonged. The method of the invention is easy to regulate and control, the process is simple and easy to amplify, and the prepared perfluorinated polymer-based composite nanofiltration membrane can be used in harsh environments such as organic solvents, high temperature and the like for a long time, thereby greatly expanding the application range of the nanofiltration membrane.
Description
Technical Field
The invention relates to the technical field of membranes, in particular to a perfluoropolymer-based composite nanofiltration membrane.
Background
Nanofiltration is a membrane process between ultrafiltration and reverse osmosis, has the characteristics of low operating pressure, high retention rate of small molecular organic matters, capability of selectively separating mono-valent ions and divalent ions, and the like, and has been widely applied to the fields of industrial water treatment, drinking water purification, medical wastewater, landfill leachate treatment, seawater desalination and the like.
Nanofiltration is mainly focused on aqueous solution systems at present, but most of the actual industrial processes involve recovery and purification of organic solvents such as methanol, dimethyl sulfoxide, acetone, chloroform and the like. In recent years, the application of nanofiltration in nonaqueous systems, such as solvent dewaxing, gasoline desulfurization, crude oil deacidification, separation and concentration of drugs, and the like, has attracted increasing attention. The application requires that the nanofiltration membrane has good stability in the corresponding organic solvent, ensures that the membrane material is not damaged by the organic solvent, and maintains stable separation effect. The most common preparation method of the nanofiltration membrane is a composite method, namely, a dense cortex part is prepared on a loose porous base membrane by coating, interfacial polymerization and other methods to form the composite nanofiltration membrane. However, the polymer nanofiltration membrane base membranes such as Polysulfone (PSF), polyethersulfone (PES), polyacrylonitrile (PAN) and the like which are commonly used at present have limited solvent resistance and high temperature resistance, and have certain limitations in practical industrial application, so that the problems to be solved are urgent.
The membrane materials of the perfluoropolymer such as polytetrafluoroethylene and the polyfluoro ethylene propylene have good mechanical property, acid and alkali resistance and also have good solvent resistance, and the perfluoropolymer is used as a composite nanofiltration membrane base membrane material to prepare the composite nanofiltration membrane, so that the membrane can be used in harsh environments such as an organic solvent and the like, and the service life of the nanofiltration membrane can be prolonged.
The nanofiber membrane prepared by the electrostatic spinning method is of a fiber interweaving structure, and has the advantages of high membrane porosity, uniform pore diameter, controllable structure and the like. However, the perfluor polymer is insoluble and infusible, so that the perfluor polymer is required to be formed into fibers by a carrier, and the carrier is removed by high-temperature sintering to obtain the continuous perfluor polymer fiber membrane. However, the membrane is severely shrunk in the carrier removal process, resulting in problems of reduced controllability of the membrane structure, membrane rupture, and the like. And the composite separation layer is hydrophilic due to strong hydrophobicity, so that the bonding strength between the base membrane and the composite layer is insufficient when the composite separation layer is directly used as a nanofiltration base membrane, the separation is easy to occur, and the service life of the membrane is seriously influenced.
In the prior art, the Chinese patent 201515581. X generates active sites by carrying out plasma treatment on a polytetrafluoroethylene membrane under the nitrogen atmosphere, then grafts polyacrylic acid, and finally assembles hydrophilic titanium dioxide on the surface of the polytetrafluoroethylene membrane to improve the hydrophilic performance and pollution resistance of the membrane, but the treatment process is complex, the requirement on equipment is high, and the stability of grafting modification under severe conditions is limited. In addition, the patent 202010125724.4 uses a hydrophobic polytetrafluoroethylene microporous membrane as a base membrane, and uses sodium dodecyl benzene sulfonate for activation, aqueous phase impregnation and oil phase impregnation, and then uses grafting reaction to generate a large amount of hydrophilic silica spherical substances, so as to obtain the anti-fouling polytetrafluoroethylene-based composite nanofiltration membrane, but the problem of the bonding strength between the base membrane and a separation layer is not solved, and the defect of insufficient stability still exists.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide the perfluoropolymer based composite nanofiltration membrane, the prepared perfluoropolymer based membrane is not easy to shrink, the structural stability is good, the perfluoropolymer based composite nanofiltration membrane and the separation layer have a stable chemical crosslinking structure, the binding force is strong, the perfluoropolymer based composite nanofiltration membrane can be used in harsh environments such as organic solvents, high temperature and the like for a long time, and the application range of the nanofiltration membrane is greatly widened.
The technical scheme adopted by the invention comprises the following steps:
step 1, preparing spinning solution:
uniformly mixing a water-soluble polymer serving as a spinning carrier with a perfluoropolymer dispersion emulsion to obtain a first component spinning solution; synthesizing a spinning solution of the co-spinning polymer or dissolving the co-spinning polymer in a solvent to obtain a spinning solution of a second component.
The water-soluble polymer is one or a combination of more of polyvinyl alcohol, gelatin, sodium alginate, polyethylene oxide and polyvinylpyrrolidone, the concentration of the carrier polymer is 5-15 wt%, and the carrier polymer is used as a sacrificial template for spinning of the perfluoropolymer.
The perfluoropolymer emulsion is one or a combination of Polytetrafluoroethylene (PTFE), fluorinated Ethylene Propylene (FEP) and tetrafluoroethylene-perfluoropropyl vinyl ether copolymer (PFA) dispersion emulsion, preferably spinning-grade PTFE dispersion emulsion.
The solid content ratio of the carrier solution to the perfluoropolymer dispersion emulsion is 1:2-1:10, preferably 1:4-1:8;
the second component spinning solution is a synthetic polyamide acid solution or a soluble polyimide solution or a mixed solution of the second component spinning solution and one of polyacrylonitrile and poly (m-phenylene isophthalamide), and the concentration is 8-15 wt%.
Step 2, preparing a perfluoropolymer-based fiber film:
and (3) respectively injecting the spinning solutions of the two components in the step (1) into an electrostatic spinning propulsion device, setting spinning parameters, taking a rotary drum (for preparing a flat membrane) or conductive filaments (for preparing a hollow fiber membrane) as a receiver, spinning the spinning solution of the first component for a period of time, then co-spinning the spinning solution of the two components for a period of time to obtain a primary flat membrane or a hollow fiber membrane, and placing the primary membrane into a muffle furnace for sintering heat treatment to obtain the perfluoropolymer-based nanofiber membrane.
The spinning solution of the first component and the second component adopts side-by-side interval or symmetrical multi-needle spinning, the ratio of the spray heads is 1:1-4:1, the first component is spun for 0-3 h, and the first component and the second component are spun together for 0.5-5 h.
The sintering is fixed-length sintering or sintering under tension, and a primary membrane is fixed by a positioning and clamping device in the sintering process.
The sintering procedure is as follows: the heating rate is set to be 1-10 ℃/min, firstly, the temperature is kept at 100 ℃ for 0.5-1.5 h, then the temperature is kept at 230-260 ℃ for 0.5-1.5 h, finally, the temperature is kept at 300-390 ℃ for 0.1-5 h, the spinning carrier is removed in the process, the perfluoropolymer particles are fused and bonded into continuous fibers, meanwhile, polyamide acid is imidized to obtain polyimide nanofibers, the polyimide nanofibers are reserved in the film, and the fibers are welded into a continuous whole.
Step 3, preparing a perfluoropolymer-based composite nanofiltration membrane:
pretreating the perfluoropolymer-based nanofiber membrane in the step 2, fixing the pretreated perfluoropolymer-based nanofiber membrane in a polypropylene frame, immersing an aqueous phase containing polyamine monomers, an interface crosslinking agent and an aqueous phase additive in the polypropylene frame for 0.5-8 min, taking out the aqueous phase, immersing the aqueous phase in an oil phase monomer solution for 10-150s after removing surface moisture, taking out the aqueous phase, and performing heat treatment at 50-80 ℃ for 2-15 min to obtain the perfluoropolymer-based composite nanofiltration membrane with the base membrane crosslinked with a surface separation layer.
The pretreatment process is to immerse the perfluorinated polymer-based nanofiber membrane in a solvent for 1-30 min, and air-dry the nanofiber membrane, wherein the solvent is one of methanol, ethanol or isopropanol or a mixed solution of the solvent and water.
The interfacial crosslinking agent is one of polyethylenimine or polyamidoamine, has the concentration of 0.2-3 w/v%, and can react with polyimide in the base film and the interfacial polymerization oil phase monomer at the same time to form a stable crosslinking structure.
The polyamine monomer is PIP, the water phase additive is hydroxylated graphene oxide or hydroxylated carbon nano tube, and the oil phase monomer solution is normal hexane oil phase solution of trimesic chloride (TMC).
Compared with the prior art, the invention has the beneficial effects that:
(1) The perfluorinated polymer nanofiber membrane prepared by the method is used as a solvent-resistant nanofiltration membrane base membrane, solves the defects that the traditional solvent-resistant nanofiltration base membrane is poor in solvent resistance and easy to swell after long-term use, improves the overall solvent resistance of the composite membrane, and expands the application range of the organic solvent nanofiltration membrane.
(2) The polyimide and the perfluorinated polymer fibers are mutually interwoven through the electrostatic spinning co-spinning polyamide acid to have an interpenetrating network structure, so that the difficult problem that the perfluorinated polymer film is contracted in the sintering process and uncontrollable in structure is solved, meanwhile, the co-spinning polyimide provides reactive sites on the surface of the film, and the defects that the perfluorinated polymer is difficult to modify, and the traditional methods such as surface coating and dipping are insufficient in modification uniformity and poor in stability are overcome.
(3) According to the invention, the perfluoro polymer blend polymer polyimide reacts with an active site in an interfacial polymerization water phase to construct chemical bond connection between the base membrane and the separation layer, so that excellent interfacial bonding strength is provided for the membrane, and the separation layer falling problem in the long-term application process of the composite membrane is solved.
(4) The perfluorinated polymer-based nanofiltration membrane base membrane prepared by the method has a multi-layer structure, the polytetrafluoroethylene fibers at the bottom layer are interwoven, the polytetrafluoroethylene fibers at the middle layer are interwoven with the polyimide fibers, and the polyamide separation layer is arranged on the surface, so that the overall permeability of the composite membrane is improved, the structure is controllable, the thickness is adjustable, the service life of the membrane is prolonged due to excellent interface bonding strength, the use cost of the membrane is reduced, and the method is easy to regulate and control, simple in process and easy to amplify.
Drawings
FIG. 1 is a scanning electron microscope image of the surface of a primary film obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the surface of the composite film obtained in example 1 of the present invention;
FIG. 3 is a photograph of a digital rose bengal photograph of the composite membrane cut-off obtained in example 1 of the present invention;
FIG. 4 is a graph showing the performance data of the composite membrane obtained in example 1 of the present invention for entrapping different dye solutions.
Detailed Description
The following describes a perfluoropolymer-based composite nanofiltration membrane and a preparation method thereof in detail by referring to the accompanying drawings and specific examples, which are only used for further detailed description of the invention, and do not limit the scope of protection of the claims of the application.
The test reagents used in the examples below, unless otherwise specified, were all commercially available and the test methods used, unless otherwise specified, were all conventional.
Example 1
Step 1, preparing spinning solution:
polyvinyl alcohol (PVA) was dissolved in 80℃water to prepare a 12 wt% PVA aqueous solution according to PVA: PTFE emulsion (solid content 60 wt%) is added into the PTFE mass ratio of 1:6 to prepare PTFE/PVA spinning solution; preparing N, N-Dimethylformamide (DMF) spinning solution of 13% polyamide acid (PAA) by using pyromellitic dianhydride (PMDA) and 4,4' -diaminodiphenyl ether (ODA) according to a molar ratio of 1:1;
step 2, preparing a perfluoropolymer-based fiber film:
injecting PTFE/PVA and PAA spinning solutions in the step 1 into an electrostatic spinning propelling device respectively, wherein a nozzle ratio of 3:2 symmetrically arranged spinning, adopting a rotary drum for receiving, and setting spinning parameters: the spinning distance is set to be 18 cm, the spinning speed of PTFE/PVA is 1 mL/h, the PAA speed is 1.5 mL/h, the spinning positive voltage is 15 kV, and the spinning negative voltage is-5 kV; the temperature is 30 ℃ and the humidity is 30%, after the PTFE/PVA solution is spun for 1h, the PTFE/PVA and the PAA spinning solution are spun together for 3 hours to obtain the primary nanofiber membrane, and the appearance of the primary nanofiber membrane is shown in figure 1. Drying in a vacuum oven at 60 ℃ for 24 hours, fixing the porous base film in a clamping device, fixing the porous base film in a fixed length, placing the porous base film in a muffle furnace, heating the porous base film from room temperature at 1 ℃/min, preserving heat at 100 ℃ for 1 hour, preserving heat at 250 ℃ for 1 hour, and finally sintering at 380 ℃ for 4 hours to obtain the bottom PTFE fiber, wherein the porous base film is basically not shrunk compared with a primary film.
Step 3, preparing a perfluoropolymer-based composite nanofiltration membrane:
soaking the base film obtained in the step 2 in ethanol for 2min, airing, fixing in a polypropylene frame, soaking in a water phase monomer solution containing 1w/v% PIP, 1w/v% PEI (polyethylenimine) and 0.03 w/v% hydroxylated graphene oxide for 2min, taking out, and removing residual water on the surface; then immersing the membrane into an n-hexane oil phase solution of trimesic acid chloride (TMC) with the concentration of 0.25 w/v%, taking out the membrane after reaction for 50s, airing the membrane, and then placing the membrane in a 70 ℃ oven for heat treatment for 8min to fully crosslink the base membrane and the separation layer, thus obtaining the PTFE-based composite nanofiltration membrane.
The molecular weight cut-off of the obtained membrane is 370 Da after testing, the cut-off rate and permeation flux of the obtained membrane on Bengalese rose bengal, methyl blue and acid fuchsin are tested under 0.5MPa, the cut-off effect on Bengalese rose bengal is shown in figure 3, the relevant test performance is shown in figure 4, and the cut-off rate of all three dyes can be seen>98%, permeation flux>55 L/m 2 H. When tested at 80 ℃, the retention rate is kept basically unchanged, and the permeation flux is increased; after the obtained membrane is soaked in methanol, toluene, ethyl acetate and dimethyl sulfoxide, the membrane flux and the rejection rate are not obviously changed, the membrane is continuously backflushed for 3 hours under the pressure of 0.3MPa, and the separation layer and the base membrane are not separated, so that the membrane has good stability and solvent resistance.
Example 2
Step 1, preparing spinning solution:
polyvinylpyrrolidone (PVP) is dissolved in water at 80 ℃ to prepare 10 wt% PVP aqueous solution, and PVP is used for preparing the aqueous solution according to the following steps: FEP emulsion (solid content 50w t%) is added into the FEP with the mass ratio of 1:8, and FEP/PVP spinning solution is prepared; polyimide P84 powder is dissolved in DMF to prepare 14 wt% PI spinning solution;
step 2, preparing a perfluoropolymer-based fiber film:
injecting FEP/PVP and PI spinning solution in the step 1 into an electrostatic spinning propelling device respectively, wherein a nozzle ratio of 3:1 side by side spinning, adopting a rotary drum to receive, and setting spinning parameters: the spinning distance is set to be 15 cm, the FEP/PVP spinning speed is 0.8 mL/h, the PI speed is 1.5 ml/h, the spinning positive voltage is 15 kV, and the spinning negative voltage is-5 kV; the temperature is 30 ℃, the humidity is 30%, and after FEP/PVP is spun for 1h, the spun yarn is spun with PI spinning solution for 3h together, and the primary nanofiber membrane is obtained. Drying in a vacuum oven at 60 ℃ for 24 hours, fixing the porous base film on a clamping device, fixing the porous base film in a fixed length, placing the porous base film in a muffle furnace, heating the porous base film from room temperature at 5 ℃/min, preserving heat at 100 ℃ for 1 hour, preserving heat at 250 ℃ for 1 hour, and finally sintering at 320 ℃ for 5 hours to obtain the porous base film with PI fibers and FEP interwoven, wherein the primary film is basically not shrunk compared with the film.
Step 3, preparing a perfluoropolymer-based composite nanofiltration membrane:
soaking the base film obtained in the step 2 in isopropanol for 5min, airing, fixing in a polypropylene frame, soaking in an aqueous monomer solution containing 1w/v% PIP, 1w/v% PAMAM (polyamidoamine) and 0.03 w/v% hydroxylated graphene oxide for 2min, taking out, and removing residual water on the surface; then immersing the membrane into normal hexane oil phase solution of TMC with the concentration of 0.25 w/v%, taking out the membrane after reacting for 50s, airing the membrane, and then placing the membrane in a 70 ℃ oven for heat treatment for 8min to fully crosslink the base membrane and the separation layer, thus obtaining the FEP-based composite nanofiltration membrane.
The molecular weight cut-off of the obtained membrane is 480 Da after testing, and the three cut-off rates of the obtained membrane on Bengal rose, methyl blue and acid fuchsin are tested under 0.5MPa>97%, permeation flux>46 L/m 2 H, testing at 80 ℃, wherein the retention rate is kept basically unchanged, the permeation flux is increased, the membrane flux and the retention rate are not obviously changed after the obtained membrane is soaked in methanol, toluene, ethyl acetate and dimethyl sulfoxide, the membrane is continuously backflushed for 3 hours under the pressure of 0.3MPa, and the separation layer is not separated from the base membrane, so that good stability and solvent resistance are shown.
Example 3
Step 1, preparing spinning solution:
dissolving PVA in water at 60 ℃ to prepare 10 wt% PVA aqueous solution, and adding PTFE emulsion (solid content is 60 wt%) into the PVA aqueous solution according to the mass ratio of PVA to PTFE of 1:8 to prepare PTFE/PVA spinning solution; polyimide P84 powder is dissolved in N, N-dimethylacetamide (DMAc) to prepare 14-wt percent PI spinning solution;
step 2, preparing a perfluoropolymer-based fiber film:
injecting PTFE/PVA and PI spinning solutions in the step 1 into an electrostatic spinning propelling device respectively, wherein a nozzle ratio of 2:1 side by side spinning, receiving by adopting a conductive filament nested glass fiber braided tube (the outer diameter is 2 mm), and setting spinning parameters: the spinning distance is set to be 15 cm, the spinning speed of PTFE/PVA is 0.8 mL/h, the PI speed is 1.5 mL/h, the spinning positive voltage is 15 kV, and the spinning negative voltage is-5 kV; the temperature is 30 ℃, the humidity is 30%, the PTFE/PVA is spun for 0.5h, and the PTFE/PVA and PI spinning solution are spun together for 0.5h to obtain a nascent nanofiber membrane. Drying in a vacuum oven at 60 ℃ for 24 hours, fixing the porous base film on a clamping device, fixing the porous base film in a fixed length, placing the porous base film in a muffle furnace, heating the porous base film from room temperature at 2 ℃/min, preserving heat at 100 ℃ for 1 hour, preserving heat at 250 ℃ for 1 hour, and finally sintering at 395 ℃ for 4 hours to obtain the porous base film with PI fibers and FEP interwoven, wherein the primary film is basically not shrunk compared with the film.
Step 3, preparing a perfluoropolymer-based composite nanofiltration membrane:
soaking the base film obtained in the step 2 in a mixed solution (4:1) of ethanol and water for 5min, airing, horizontally fixing on a polypropylene bracket, immersing in a water-phase monomer solution containing 2 w/v% PIP, 1w/v% PEI and 0.03 w/v% hydroxylated carbon nano tube for 2min, taking out, and removing residual water on the surface; then immersing the membrane into normal hexane oil phase solution of TMC with the concentration of 0.35 w/v%, taking out the membrane after reacting for 50s, airing the membrane, and then placing the membrane in a 70 ℃ oven for heat treatment for 8min to fully crosslink the base membrane and the separation layer, thus obtaining the PTFE-based hollow fiber membrane composite nanofiltration membrane.
The molecular weight cut-off of the obtained membrane is 570 Da, and the three dye cut-off rates of the obtained membrane on Bengal rose, methyl blue and acid fuchsin are tested under 0.5MPa>90%, permeation flux>52 L/m 2 H, testing at 80 ℃, wherein the retention rate is kept basically unchanged, the permeation flux is increased, the membrane flux and the retention rate are not obviously changed after the obtained membrane is soaked in methanol, toluene, ethyl acetate and dimethyl sulfoxide, the membrane is continuously backflushed for 3 hours under the pressure of 0.3MPa, and the separation layer is not separated from the base membrane, so that good stability and solvent resistance are shown.
Example 4
Step 1, preparing spinning solution:
gelatin is dissolved in water at 60 ℃ to prepare 10 wt% gelatin water solution, and the gelatin is prepared by the following steps: PFA emulsion (solid content 50 wt%) is added into the PFA mass ratio of 1:8 to prepare PFA/gelatin spinning solution; polyimide P84 powder and polyacrylonitrile (1:1) are dissolved in DMAc to prepare 13 wt percent PI/PAN spinning solution;
step 2, preparing a perfluoropolymer-based fiber film:
injecting the PFA/gelatin and PI/PAN spinning solutions in the step 1 into an electrostatic spinning propulsion device respectively, wherein a nozzle ratio of 3 is adopted: 1, symmetrical spinning, adopting a rotating roller for receiving, and setting spinning parameters: the spinning distance is set to 15 cm, the PFA/gelatin spinning speed is 1.2 mL/h, the PI/PAN speed is 1.0 mL/h, the spinning positive voltage is 18 kV, and the spinning negative voltage is-5 kV; the temperature is 30 ℃, the humidity is 30 percent, and the spun nano fiber film is obtained after the PFA/gelatin and PI/PAN spinning solution are spun together for 3 hours. Drying in a vacuum oven at 60 ℃ for 24 hours, fixing the porous base film on a clamping device, fixing the porous base film in a fixed length, placing the porous base film in a muffle furnace, heating the porous base film from room temperature at 2 ℃/min, preserving heat at 100 ℃ for 1 hour, preserving heat at 250 ℃ for 1 hour, and finally sintering at 395 ℃ for 4 hours to obtain the porous base film with PI/PAN fibers and PFA fibers, wherein the primary film is basically not shrunk compared with the primary film.
Step 3, preparing a perfluoropolymer-based composite nanofiltration membrane:
immersing the base film obtained in the step 2 in isopropanol for 10min, airing, fixing in a polypropylene frame, immersing in a water phase monomer solution containing 2 w/v% PIP, 1w/v% PEI and 0.03 w/v% hydroxylated carbon nano tube for 2min, taking out, and removing residual water on the surface; then immersing the membrane into normal hexane oil phase solution of TMC with the concentration of 0.35 w/v%, taking out the membrane after reacting for 50s, airing the membrane, and then placing the membrane in an oven with the temperature of 80 ℃ for heat treatment for 5min to fully crosslink the base membrane and the separation layer, thus obtaining the PFA-based hollow fiber membrane composite nanofiltration membrane.
The membrane obtained by the test has the molecular weight cut-off of 520 Da and the cut-off rates of Bengal rose bengal, methyl blue and acid fuchsin under 0.5MPa>92%, permeation flux>45 L/m 2 H, testing at 80 ℃, wherein the retention rate is kept basically unchanged, the permeation flux is increased, the membrane flux and the retention rate are not obviously changed after the obtained membrane is soaked in methanol, toluene, ethyl acetate and dimethyl sulfoxide, the membrane is continuously backflushed for 3 hours under the pressure of 0.3MPa, and the separation layer is not separated from the base membrane, so that good stability and solvent resistance are shown.
The specific examples above show that the invention solves the defects of poor solvent resistance and easy swelling after long-term use of the traditional solvent-resistant nanofiltration base film, and improves the overall solvent resistance of the composite film. The invention forms an interpenetrating network structure by the polyimide and the perfluorinated polymer fibers, overcomes the problems of shrinkage and uncontrollable structure of the perfluorinated polymer membrane in the sintering process, and simultaneously provides reactive sites on the membrane surface by the co-spinning polyimide, thereby solving the problems of difficult modification of the perfluorinated polymer, and the defects of insufficient modification uniformity, poor stability and the like of the traditional surface coating, dipping and other methods. In addition, the invention utilizes the reaction of the perfluorinated polymer blend polymer polyimide and the active site in the interfacial polymerization water phase to construct the chemical bond connection between the base membrane and the separation layer, thus endowing the membrane with excellent interfacial bonding strength.
While the present invention has been described with reference to the foregoing embodiments, those skilled in the art will understand that various specific parameters in the foregoing embodiments may be changed without departing from the spirit of the invention, and that the present invention is not limited to the specific embodiments, which are common and varied.
Claims (7)
1. The perfluoropolymer based composite nanofiltration membrane is characterized in that the perfluoropolymer based composite nanofiltration membrane is prepared by the following method, and the method comprises the following steps:
step 1, preparing spinning solution: uniformly mixing a water-soluble polymer serving as a carrier with a perfluoropolymer dispersion emulsion to obtain a first component spinning solution, and dissolving a co-spinning polymer in a solvent to obtain a second component spinning solution;
step 2, preparing a perfluoropolymer-based nanofiber membrane: respectively injecting the spinning solutions of the two components in the step 1 into an electrostatic spinning propulsion device, setting spinning parameters, taking a rotary drum or a conductive filament as a receiver, spinning the spinning solution of the first component for a period of time, then co-spinning the spinning solution of the two components for a period of time to obtain a primary flat membrane or a hollow fiber membrane, and placing the primary membrane into a muffle furnace for sintering heat treatment to obtain a perfluoropolymer-based nanofiber membrane;
step 3, preparing a perfluoropolymer-based composite nanofiltration membrane: pretreating the perfluoropolymer-based nanofiber membrane obtained in the step 2, fixing the pretreated perfluoropolymer-based nanofiber membrane in a polypropylene frame, immersing an aqueous phase solution containing polyamine monomers, an interface crosslinking agent and an aqueous phase additive in the polypropylene frame, taking out the aqueous phase solution after 0.5-8 min, immersing the aqueous phase solution in an oil phase monomer solution after removing surface moisture, taking out the aqueous phase solution after 10-150s, and carrying out heat treatment at 50-80 ℃ for 2-15 min to obtain the perfluoropolymer-based composite nanofiltration membrane with a crosslinking structure of a base membrane and a surface separation layer;
wherein the water-soluble polymer in the step 1 is one or a combination of more of gelatin, polyethylene oxide (PEO) and polyvinylpyrrolidone (PVP), and the concentration of the water-soluble polymer is 5-15 wt% and is used as a sacrificial template for perfluorinated polymer spinning;
the perfluoropolymer dispersion emulsion is one or a combination of more than one of Polytetrafluoroethylene (PTFE), fluorinated Ethylene Propylene (FEP) and tetrafluoroethylene-perfluoropropyl vinyl ether copolymer dispersion emulsion;
the co-spinning polymer is any one of polyamide acid, polyacrylonitrile, soluble polyimide, poly m-phenylene isophthalamide and poly p-phenylene terephthalamide, and the concentration is 8-15 wt%;
the solid content ratio of the water-soluble polymer to the perfluoropolymer dispersion emulsion is 1:2-10;
the interfacial crosslinking agent is one of polyethylenimine or polyamidoamine PAMAM, the concentration is 0.2-3 w/v%, and the interfacial crosslinking agent can simultaneously react with the co-spinning polymer and the interfacial polymerization oil phase monomer in the base film to form a stable chemical crosslinking structure;
and 3, wherein the polyamine monomer is PIP, the water phase additive is hydroxylated graphene oxide or hydroxylated carbon nano tube, and the oil phase monomer solution is normal hexane oil phase solution of trimesoyl chloride.
2. The perfluoropolymer-based composite nanofiltration membrane of claim 1, wherein the perfluoropolymer dispersion emulsion of step 1 is a PTFE dispersion emulsion; the co-spun polymer is a polyamic acid.
3. The perfluoropolymer-based composite nanofiltration membrane according to claim 1, wherein the solid content ratio of the water-soluble polymer to the perfluoropolymer dispersion emulsion in the step 1 is 1:4-8.
4. The perfluoropolymer matrix composite nanofiltration membrane of claim 1, wherein in step 2 the first component spinning solution and the second component spinning solution are spun by adopting a plurality of needles side by side or symmetrically, the ratio of the spray heads is 1-4:1, the first component spinning solution is spun for 0.5-3 hours, and the first component spinning solution and the second component spinning solution are spun together for 0.5-3 hours.
5. The perfluoropolymer based composite nanofiltration membrane of claim 1, wherein the sintering in step 2 is a fixed length sintering, wherein the as-sintered membrane is held by a positioning and clamping device.
6. The perfluoropolymer based composite nanofiltration membrane of claim 1, wherein the sintering heat treatment procedure of step 2 is: the heating rate is set to be 1-10 ℃/min, firstly, the temperature is kept at 100 ℃ for 0.5-1.5 h, then the temperature is kept at 230-260 ℃ for 0.5-1.5 h, finally, the temperature is kept at 300-390 ℃ for 0.1-5 h, the spinning carrier is removed, the perfluoropolymer particles are bonded into continuous fibers, meanwhile, the co-spun polymer remains in the film after imidization, and the fibers are welded into a continuous whole.
7. The perfluoropolymer based composite nanofiltration membrane according to claim 1, wherein the pretreatment process in step 3 is to impregnate the perfluoropolymer based nanofiber membrane in a solvent for 1-30 min, and air-dry, wherein the solvent is one of methanol, ethanol or isopropanol or a mixed solution with water.
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