CN116272433B - Modified polyvinylidene fluoride water treatment film and preparation method thereof - Google Patents
Modified polyvinylidene fluoride water treatment film and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 106
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000012528 membrane Substances 0.000 claims abstract description 88
- 229920002492 poly(sulfone) Chemical group 0.000 claims abstract description 48
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920000412 polyarylene Polymers 0.000 claims abstract description 20
- -1 sulfide sulfone Chemical class 0.000 claims abstract description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 238000005406 washing Methods 0.000 claims description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 38
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 38
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 239000000706 filtrate Substances 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 238000001291 vacuum drying Methods 0.000 claims description 27
- 239000012510 hollow fiber Substances 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 22
- 239000012044 organic layer Substances 0.000 claims description 21
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 19
- KMMHZIBWCXYAAH-UHFFFAOYSA-N 4-bromobenzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=C(Br)C=C1 KMMHZIBWCXYAAH-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 229940078552 o-xylene Drugs 0.000 claims description 18
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 17
- 239000013067 intermediate product Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 13
- 238000009987 spinning Methods 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000008118 PEG 6000 Substances 0.000 claims description 8
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 5
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000004907 flux Effects 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 229920005597 polymer membrane Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 48
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 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
- 230000000903 blocking effect Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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 provides a modified polyvinylidene fluoride water treatment membrane and a preparation method thereof, and relates to the technical field of polymer membrane materials; the modified polyvinylidene fluoride water treatment film comprises the following components in parts by weight: 20-30 parts of polyvinylidene fluoride; 5-15 parts of polyarylene sulfide sulfone; 1-3 parts of a compatibilizer containing a fluorocarbon chain and a polysulfone structure; 1.5 parts of PEG; 50.5-72.5 parts of dimethylacetamide. According to the modified polyvinylidene fluoride water treatment membrane provided by the invention, the compatibilizer with the fluorocarbon chain and polysulfone structure is introduced, namely the compatibilizer structure contains the fluorocarbon chain and polysulfone structure, and according to the similar compatibility principle, the compatibilizer can be effectively compatible with a polyvinylidene fluoride phase and a polysulfone phase, so that the compatibility is improved, and a homogeneous structure is formed, so that the water flux is improved, the water treatment effect is ensured, the mechanical property of the membrane is improved, the membrane strength is improved, the water treatment membrane can bear high-frequency shaking, and the service life of a material is effectively prolonged.
Description
Technical Field
The invention relates to the technical field of polymer membrane materials, in particular to a modified polyvinylidene fluoride water treatment membrane and a preparation method thereof.
Background
The membrane technology is called a '21 st century water treatment technology', has a remarkable enhancement on the effect of reducing environmental pollution, and has gradually exerted its technical advantages in the industries of chemical engineering, energy sources, medicines, electronics and the like. The membrane technology is used for treating wastewater and has unique technical advantages: by selecting proper membrane materials and component forms, the pH value and pretreatment are not required to be adjusted; the waste liquid is not required to be destroyed, and the running cost is reduced. However, the application efficiency of membrane technology for wastewater treatment is severely limited by the bottleneck problem of membrane pollution, and flux attenuation is serious. The membrane pollution is mainly caused by adsorption, deposition and membrane pore blocking of oil drops on the membrane surface and the membrane pore surface and concentration polarization phenomenon. In order to maintain normal water production of the membrane, the membrane must withstand high intensity aeration shaking in order to mitigate sludge clogging; that is, the water treatment film is required to have higher strength, better resistance to microbial contamination, and stronger resistance to cleaning by chemicals such as acid and alkali.
As a common material in water treatment membranes, polyvinylidene fluoride (PVDF) has a molecular structure connected end to end, and because of the regularity of the molecular structure arrangement and higher bond energy of C-F bonds, the membranes with good performances in the aspects of temperature resistance, corrosion resistance and the like can be manufactured by controlling the process conditions; however, because polyvinylidene fluoride has extremely strong hydrophobicity, the water treatment membrane prepared from the polyvinylidene fluoride is easy to adsorb pollutants so as to block the fiber membrane, reduce the membrane flux and influence the water treatment effect; based on this, a blend film of polyvinylidene fluoride (PVDF) and polyarylene sulfide sulfone (PASS) materials has attracted some scholars' attention as a blend means; the blending modification can make up the defect of a single component in specific performance to a certain extent, and the method is easy to operate, has obvious effect and is an ideal method for modifying the film. Through the blending of polyvinylidene fluoride (PVDF) and polyarylene sulfide sulfone (PASS) materials, the water treatment effect can be improved to a certain extent, but the mechanical property of the water treatment film prepared by blending the polyvinylidene fluoride (PVDF) and the PVDF is poor due to the fact that the solubility parameters of the polyarylene sulfide sulfone and the PVDF are large in difference and poor in compatibility, the phenomenon of breakage and breakage easily occurs due to aeration shake in the use process, the water treatment effect is affected, the service life of the water treatment film is shortened, and the cost is increased.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to solve the problem of poor compatibility of polyvinylidene fluoride and polyarylene sulfide sulfone in the prior art, the invention provides a modified polyvinylidene fluoride water treatment membrane which is effectively compatible with a polyvinylidene fluoride phase and a polysulfone phase by introducing a compatibilizer containing a fluorocarbon chain and a polysulfone structure to form a homogeneous structure, thereby solving the problem of poor compatibility of polyvinylidene fluoride and polyarylene sulfide sulfone.
The technical scheme adopted for solving the technical problems is as follows:
the modified polyvinylidene fluoride water treatment film comprises the following components in parts by weight:
optionally, the compatibilizer containing fluorocarbon chains and polysulfone structures is prepared according to the following method:
s01: 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine and 4-dimethylaminopyridine are dissolved in dichloromethane and stirred for 12 to 20 hours at room temperature; after the reaction is finished, washing with hydrochloric acid solution and deionized water in sequence, separating liquid, taking an organic layer, drying, filtering, distilling filtrate under reduced pressure, and vacuum drying at 60 ℃ for 8 hours to obtain an intermediate product I;
s02: adding o-xylene into a reaction kettle, stirring, introducing nitrogen, adding bisphenol S and sodium hydroxide, heating at 80-100 ℃ for 2-3h, continuously heating and refluxing until the water discharged from a water separator is constant weight, cooling to room temperature, adding dimethyl sulfoxide and an intermediate product I, heating to 140-160 ℃ and stirring for 4-8h, cooling to 110 ℃, stopping introducing nitrogen, filtering, taking filtrate, respectively washing with hydrochloric acid solution and deionized water, separating liquid, taking an organic layer, drying, filtering, decompressing and distilling the filtrate, and vacuum-drying at 60 ℃ for 8h to obtain the compatibilizer with a fluorine-containing carbon chain and polysulfone structure.
Alternatively, the 1H, 1H-perfluorononyl-1-ol, 4-bromobenzenesulfonyl chloride and triethylamine are used in the amount ratio of 1mol in step S01: 1mol:1.4mol; the dosage of the 4-dimethylaminopyridine is 0.15% of the total mass of the reactants.
Alternatively, the dosage ratio of ortho-xylene, bisphenol S, sodium hydroxide, dimethyl sulfoxide, intermediate I in step S02 is 600mL:0.5mol:1.2mol:500mL:1mol.
Optionally, the PEG is PEG4000, PEG6000 or PEG8000.
Another object of the present invention is to provide a method for preparing the modified polyvinylidene fluoride water treatment film as described above, comprising the steps of:
s1: the preparation method comprises the steps of (1) keeping constant temperature for 24 hours at 60 ℃ for polyvinylidene fluoride, polyarylene sulfide sulfone, a compatibilizer containing fluorocarbon chains and polysulfone structures, PEG and dimethylacetamide, adding the raw materials into a batching kettle according to a proportion, stirring for 10 hours at 150 ℃, cooling a dissolved high polymer solution to room temperature at 200rpm, vacuum drying for 8 hours at 60 ℃, and crushing for later use;
s2: putting the crushed raw materials in the step S1 into a double-screw extruder, carrying out melt blending at the temperature of 150-190 ℃ and the rotating speed of 120-150rpm, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen as a pressure source to form a hollow fiber membrane;
s3: and (3) washing the hollow fiber membrane in the step (S2) with water and alcohol, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
Optionally, the temperature parameters of each zone of the extruder are 150-170 ℃, 160-180 ℃, 170-190 ℃, 180-190 ℃ and 180-190 ℃.
Optionally, the spinneret parameters of the extruder: an inner diameter of 4.0mm and an outer diameter of 4.5mm; nitrogen pressure: 0.05-0.15MPa.
Optionally, the water washing process in the step S3 is soaking for 2 hours at the temperature of 10-50 ℃ and washing for 1 hour.
Optionally, the alcohol washing process in the step S3 is soaking for 2 hours at room temperature and washing for 1 hour.
The beneficial effects of the invention are as follows:
according to the modified polyvinylidene fluoride water treatment membrane provided by the invention, on one hand, the compatibilizer with the fluorocarbon chain and polysulfone structure is introduced, namely the compatibilizer structure contains the fluorocarbon chain and polysulfone structure at the same time, and according to the similar compatibility principle, the compatibilizer can be effectively compatible with a polyvinylidene fluoride phase and a polysulfone phase, so that the compatibility is improved, and a homogeneous structure is formed, so that the water flux is improved, the water treatment effect is ensured, the mechanical property of the membrane is improved, the membrane strength is improved, the water treatment membrane can bear high-frequency shaking, and the service life of materials is effectively prolonged; on the other hand, in the formula system provided by the invention, the macromolecular chain containing the PEG structure has larger chain entanglement, so that the compatibility of the matrix material can be improved in an auxiliary manner, and the PEG has excellent water solubility, so that the water flux of the modified polyvinylidene fluoride water treatment membrane can be greatly improved; meanwhile, the dimethylacetamide in the formula system provided by the invention is used as a good solvent for polyvinylidene fluoride and polysulfone, and the further compatibility of the matrix material is effectively promoted.
Detailed Description
The present invention will now be described in further detail. The embodiments described below are exemplary and intended to illustrate the invention and should not be construed as limiting the invention, as all other embodiments, based on which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of the invention.
In order to solve the problem of poor compatibility of polyvinylidene fluoride and polyarylene sulfide sulfone in the prior art, the invention provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
according to the modified polyvinylidene fluoride water treatment membrane provided by the invention, on one hand, the compatibilizer with the fluorocarbon chain and polysulfone structure is introduced, namely the compatibilizer structure contains the fluorocarbon chain and polysulfone structure at the same time, and according to the similar compatibility principle, the compatibilizer can be effectively compatible with a polyvinylidene fluoride phase and a polysulfone phase, so that the compatibility is improved, and a homogeneous structure is formed, so that the water flux is improved, the water treatment effect is ensured, the mechanical property of the membrane is improved, the membrane strength is improved, the water treatment membrane can bear high-frequency shaking, and the service life of materials is effectively prolonged; on the other hand, in the formula system provided by the invention, the macromolecular chain containing the PEG structure has larger chain entanglement, so that the compatibility of the matrix material can be improved in an auxiliary manner, and the PEG has excellent water solubility, so that the water flux of the modified polyvinylidene fluoride water treatment membrane can be greatly improved; meanwhile, the dimethylacetamide in the formula system provided by the invention is used as a good solvent for polyvinylidene fluoride and polysulfone, and the further compatibility of the matrix material is effectively promoted.
Specifically, the compatibilizer with the fluorocarbon chain and polysulfone structure is preferably prepared according to the following method:
s01: 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine and 4-dimethylaminopyridine are dissolved in dichloromethane and stirred for 12 to 20 hours at room temperature; after the reaction is finished, washing with hydrochloric acid solution and deionized water in sequence, separating liquid, taking an organic layer, drying, filtering, distilling filtrate under reduced pressure, and vacuum drying at 60 ℃ for 8 hours to obtain an intermediate product I;
s02: adding o-xylene into a reaction kettle, stirring, introducing nitrogen, adding bisphenol S and sodium hydroxide, heating at 80-100 ℃ for 2-3h, continuously heating and refluxing until the water separated from a water separator is constant weight, cooling to room temperature, adding dimethyl sulfoxide and an intermediate product I, heating to 140-160 ℃ and stirring for 4-8h, cooling to 110 ℃, stopping introducing nitrogen, filtering, taking filtrate, respectively washing with hydrochloric acid solution and deionized water, separating liquid, taking an organic layer, drying, filtering, decompressing and distilling the filtrate, and vacuum-drying at 60 ℃ for 8h to obtain a target product II, namely the compatibilizer with a fluorine-containing carbon chain and polysulfone structure.
The preparation process is as follows:
through the process, the fluorine-containing carbon chain and the polysulfone structure are simultaneously introduced into the molecular structure of the compatibilizer, so that the compatibilizer can be effectively compatible with polyvinylidene fluoride phase and polysulfone phase, the compatibility is improved, and a homogeneous structure is formed, thereby improving the water flux, ensuring the water treatment effect, improving the mechanical property of the membrane and improving the membrane strength.
In order to ensure the compatibility of the compatibilizer, the invention preferably uses 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride and triethylamine in the amount ratio of 1mol in the step S01: 1mol:1.4mol; preferably, after the reaction in this step is completed, the organic layer is dried over anhydrous sodium sulfate by washing with 1M hydrochloric acid solution 2 times, deionized water 2 times and separating the solution, and more preferably, 1H-perfluorononyl-1-ol, 4-bromobenzenesulfonyl chloride, triethylamine, dichloromethane, hydrochloric acid solution, deionized water and anhydrous sodium sulfate are used in an amount ratio of 1mol:1mol:1.4mol:1200mL:1000mL:1000mL:80g; preferably, the amount of 4-dimethylaminopyridine is 0.15% of the total mass of the reactants; preferably, the dosage ratio of o-xylene, bisphenol S, sodium hydroxide, dimethyl sulfoxide and intermediate I in the step S02 is 600mL:0.5mol:1.2mol:500mL:1mol; preferably, the filtrate is filtered and taken in the step, and then is respectively washed with 1M hydrochloric acid solution for 2 times and deionized water for 2 times, the organic layer is separated, and the organic layer is dried with anhydrous sodium sulfate; and further preferably, the dosage ratio of o-xylene, bisphenol S, sodium hydroxide, dimethyl sulfoxide, intermediate I, hydrochloric acid solution, deionized water and anhydrous sodium sulfate in the step is 600mL:0.5mol:1.2mol:500mL:1mol:600mL:600mL:80g.
In order to further improve the compatibility, the PEG is preferably PEG4000, PEG6000 or PEG8000.
Another object of the present invention is to provide a method for preparing the modified polyvinylidene fluoride water treatment film as described above, comprising the steps of:
s1: the preparation method comprises the steps of (1) keeping constant temperature for 24 hours at 60 ℃ for polyvinylidene fluoride, polyarylene sulfide sulfone, a compatibilizer containing fluorocarbon chains and polysulfone structures, PEG and dimethylacetamide, adding the raw materials into a batching kettle according to a proportion, stirring for 10 hours at 150 ℃, cooling a dissolved high polymer solution to room temperature at 200rpm, vacuum drying for 8 hours at 60 ℃, and crushing for later use;
s2: putting the crushed raw materials in the step S1 into a double-screw extruder, carrying out melt blending at the temperature of 150-190 ℃ and the rotating speed of 120-150rpm, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen as a pressure source to form a hollow fiber membrane;
s3: and (3) washing the hollow fiber membrane in the step (S2) with water and alcohol, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
According to the preparation method of the modified polyvinylidene fluoride water treatment membrane, firstly, after being modified by the compatibilizer, the material is uniformly dispersed, the temperature is low in floating, and uniform membrane materials are formed; secondly, after extrusion by an extruder, stretching spinning and material orientation, the mechanical property can be further improved; the prepared modified polyvinylidene fluoride water treatment membrane improves the water flux, ensures the water treatment effect, improves the mechanical property of the membrane and the membrane strength, so that the water treatment membrane can bear high-frequency shaking, and effectively prolongs the service life of the material.
Specifically, in order to consider the water treatment effect and mechanical properties of the modified polyvinylidene fluoride water treatment film, the temperature parameters of each region of the extruder are 150-170 ℃, 160-180 ℃, 170-190 ℃, 180-190 ℃ and 180-190 ℃ preferably; spinneret parameters of extruder: an inner diameter of 4.0mm and an outer diameter of 4.5mm; nitrogen pressure: 0.05-0.15MPa; the water washing process in the step S3 is that soaking is carried out for 2 hours at the temperature of 10-50 ℃ and washing is carried out for 1 hour; the alcohol washing process in the step S3 is soaking for 2 hours at room temperature and washing for 1 hour.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
Example 1
The embodiment provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer containing fluorocarbon chains and polysulfone structures comprises the following steps:
s01: 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine and 4-dimethylaminopyridine are dissolved in dichloromethane and stirred for 16h at room temperature; after the reaction is finished, washing with 1M hydrochloric acid solution for 2 times, washing with deionized water for 2 times, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and vacuum drying at 60 ℃ for 8 hours to obtain an intermediate product I;
the dosage ratio of the 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine, methylene dichloride, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 1mol:1mol:1.4mol:1200mL:1000mL:1000mL:80g;
the dosage of the 4-dimethylaminopyridine is 0.15% of the total mass of the reactants;
intermediate I infrared data are as follows: 3520cm -1 : -OH vanishes; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br is present;
s02: adding o-xylene into a reaction kettle, stirring, introducing nitrogen, adding bisphenol S and sodium hydroxide, heating at 90 ℃ for 2.5h, continuously heating and refluxing until the water discharged from a water separator is constant weight, cooling to room temperature, adding dimethyl sulfoxide and an intermediate product I, heating to 150 ℃ and stirring for 6h, cooling to 110 ℃, stopping ventilation, filtering, taking filtrate, respectively washing 2 times with 1M hydrochloric acid solution, washing 2 times with deionized water B, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, carrying out reduced pressure distillation on the filtrate, and carrying out vacuum drying at 60 ℃ for 8h to obtain a target product II, namely the compatibilizer with a fluorine-containing carbon chain and polysulfone structure;
the dosage ratio of the o-xylene, bisphenol S, sodium hydroxide, dimethyl sulfoxide, intermediate I, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 600mL:0.5mol:1.2mol:500mL:1mol:600mL:600mL:80g;
the infrared data for target product II are as follows: 3520cm -1 : -OH is absent; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br disappeared.
The nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CD 3 CN, δppm): 7.3-8.2 (16H, benzene ring); 4.59 (4H, -CH) 2 -)。
The preparation method of the modified polyvinylidene fluoride water treatment film in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of (1) keeping constant temperature of polyvinylidene fluoride, polyarylene sulfide sulfone, a compatibilizer containing fluorocarbon chains and polysulfone structures, PEG6000 and dimethylacetamide for 24 hours at 60 ℃, adding the raw materials into a batching kettle according to a proportion, stirring for 10 hours at 150 ℃, cooling a dissolved high polymer solution to room temperature at 200rpm, vacuum drying for 8 hours at 60 ℃, and crushing for later use;
s2: putting the raw materials in the step S1 into a double-screw extruder, respectively carrying out melt blending at the temperature of 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ and 130rpm of screw speed in each region, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen of 0.10MPa as a pressure source to form a hollow fiber membrane; spinneret parameters: an inner diameter of 4.0mm and an outer diameter of 4.5mm;
s3: soaking the hollow fiber membrane in the step S2 in water at 50 ℃ for 2h, washing for 1h, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
Example 2
The embodiment provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer containing fluorocarbon chains and polysulfone structures comprises the following steps:
s01: 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine and 4-dimethylaminopyridine are dissolved in dichloromethane and stirred for 20h at room temperature; after the reaction is finished, washing with 1M hydrochloric acid solution for 2 times, washing with deionized water for 2 times, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and vacuum drying at 60 ℃ for 8 hours to obtain an intermediate product I;
the dosage ratio of the 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine, methylene dichloride, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 1mol:1mol:1.4mol:1200mL:1000mL:1000mL:80g;
the dosage of the 4-dimethylaminopyridine is 0.15% of the total mass of the reactants;
intermediate I infrared data are as follows: 3520cm -1 : -OH vanishes; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br is present.
S02: adding o-xylene into a reaction kettle, stirring, introducing nitrogen, adding bisphenol S and sodium hydroxide, heating at 80 ℃ for 3 hours, continuously heating and refluxing until the water discharged from a water separator is constant, cooling to room temperature, adding dimethyl sulfoxide and an intermediate product I, heating to 140 ℃ and stirring for 8 hours, cooling to 110 ℃, stopping ventilation, filtering, taking filtrate, respectively washing with 1M hydrochloric acid solution for 2 times, washing with deionized water for 2 times, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, decompressing and distilling the filtrate, and vacuum drying at 60 ℃ for 8 hours to obtain a target product II;
the dosage ratio of the o-xylene, bisphenol S, sodium hydroxide, dimethyl sulfoxide, intermediate I, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 600mL:0.5mol:1.2mol:500mL:1mol:600mL:600mL:80g;
the infrared data for target product II are as follows: 3520cm -1 : -OH is absent; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br disappeared.
The nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CD 3 CN, δppm): 7.3-8.2 (16H, benzene ring); 4.59 (4H, -CH) 2 -)。
The preparation method of the modified polyvinylidene fluoride water treatment film in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of (1) keeping constant temperature of polyvinylidene fluoride, polyarylene sulfide sulfone, a compatibilizer containing fluorocarbon chains and polysulfone structures, PEG8000 and dimethylacetamide at 60 ℃ for 24 hours, adding the raw materials into a batching kettle according to a proportion, stirring for 10 hours at 150 ℃, cooling a dissolved high polymer solution to room temperature at 200rpm, vacuum drying for 8 hours at 60 ℃, and crushing for later use;
s2: putting the raw materials in the step S1 into a double-screw extruder, respectively carrying out melt blending at 160 ℃ and 160 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ and 185 ℃ in each region and at a screw speed of 120rpm, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen of 0.05MPa as a pressure source to form a hollow fiber membrane; spinneret parameters: an inner diameter of 4.0mm and an outer diameter of 4.5mm;
s3: soaking the hollow fiber membrane in the step S2 in water at 10 ℃ for 2h, washing for 1h, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
Example 3
The embodiment provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer containing fluorocarbon chains and polysulfone structures comprises the following steps:
s01: 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine and 4-dimethylaminopyridine are dissolved in dichloromethane and stirred for 12h at room temperature; washing with 1M hydrochloric acid solution for 2 times, washing with deionized water for 2 times, separating, collecting organic layer, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and vacuum drying at 60deg.C for 8 hr to obtain intermediate I;
the dosage ratio of the 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine, methylene dichloride, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 1mol:1mol:1.4mol:1200mL:1000mL:1000mL:80g;
the dosage of the 4-dimethylaminopyridine is 0.15% of the total mass of the reactants;
intermediate I infrared data are as follows: 3520cm -1 : -OH vanishes; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br is present.
S02: adding o-xylene into a reaction kettle, stirring, introducing nitrogen, adding bisphenol S and sodium hydroxide, heating at 100 ℃ for 2 hours, continuously heating and refluxing until the water discharged from a water separator is constant, cooling to room temperature, adding dimethyl sulfoxide and an intermediate product I, heating to 160 ℃ and stirring for 4 hours, cooling to 110 ℃, stopping ventilation, filtering, taking filtrate, respectively washing with 1M hydrochloric acid solution for 2 times, washing with deionized water for 2 times, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, decompressing and distilling the filtrate, and vacuum drying at 60 ℃ for 8 hours to obtain a target product II;
the dosage ratio of the o-xylene, bisphenol S, sodium hydroxide, dimethyl sulfoxide, intermediate I, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 600mL:0.5mol:1.2mol:500mL:1mol:600mL:600mL:80g;
the infrared data for target product II are as follows: 3520cm -1 : -OH is absent; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br disappeared;
the nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CD 3 CN, δppm): 7.3-8.2 (16H, benzene ring); 4.59 (4H, -CH) 2 -)；
The preparation method of the modified polyvinylidene fluoride water treatment film in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of (1) keeping constant temperature of polyvinylidene fluoride, polyarylene sulfide sulfone, a compatibilizer containing fluorocarbon chains and polysulfone structures, PEG4000 and dimethylacetamide at 60 ℃ for 24 hours, adding the raw materials into a batching kettle according to a proportion, stirring for 10 hours at 150 ℃, cooling a dissolved high polymer solution to room temperature at 200rpm, vacuum drying for 8 hours at 60 ℃, and crushing for later use;
s2: putting the raw materials in the step S1 into a double-screw extruder, respectively carrying out melt blending at the temperature of 170 ℃, 180 ℃, 185 ℃, 190 ℃ and the screw rotation speed of 150rpm in each region, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen of 0.15MPa as a pressure source to form a hollow fiber membrane; spinneret parameters: an inner diameter of 4.0mm and an outer diameter of 4.5mm;
s3: soaking the hollow fiber membrane in the step S2 in water at 40 ℃ for 2h, washing for 1h, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
Example 4
The embodiment provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer containing fluorocarbon chains and polysulfone structures comprises the following steps:
s01: 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine and 4-dimethylaminopyridine are dissolved in dichloromethane and stirred for 14h at room temperature; after the reaction is finished, washing with 1M hydrochloric acid solution for 2 times, washing with deionized water for 2 times, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and vacuum drying at 60 ℃ for 8 hours to obtain an intermediate product I;
the dosage ratio of the 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine, methylene dichloride, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 1mol:1mol:1.4mol:1200mL:1000mL:1000mL:80g;
the dosage of the 4-dimethylaminopyridine is 0.15% of the total mass of the reactants;
intermediate I infrared data are as follows: 3520cm -1 : -OH vanishes; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br is present;
s02: adding o-xylene into a reaction kettle, stirring, introducing nitrogen, adding bisphenol S and sodium hydroxide, heating at 90 ℃ for 2 hours, continuously heating and refluxing until the water discharged from a water separator is constant in weight, cooling to room temperature, adding dimethyl sulfoxide and an intermediate product I, heating to 150 ℃ and stirring for 8 hours, cooling to 110 ℃, stopping ventilation, filtering, taking filtrate, respectively washing with 1M hydrochloric acid solution for 2 times, washing with deionized water for 2 times, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, decompressing and distilling the filtrate, and vacuum-drying at 60 ℃ for 8 hours to obtain a target product II;
the dosage ratio of the o-xylene, bisphenol S, sodium hydroxide, dimethyl sulfoxide, intermediate I, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 600mL:0.5mol:1.2mol:500mL:1mol:600mL:600mL:80g;
the infrared data for target product II are as follows: 3520cm -1 : -OH is absent; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br disappeared;
the nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CD 3 CN, δppm): 7.3-8.2 (16H, benzene ring); 4.59 (4H, -CH) 2 -)；
The preparation method of the modified polyvinylidene fluoride water treatment film in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of (1) keeping constant temperature of polyvinylidene fluoride, polyarylene sulfide sulfone, a compatibilizer containing fluorocarbon chains and polysulfone structures, PEG8000 and dimethylacetamide at 60 ℃ for 24 hours, adding the raw materials into a batching kettle according to a proportion, stirring for 10 hours at 150 ℃, cooling a dissolved high polymer solution to room temperature at 200rpm, vacuum drying for 8 hours at 60 ℃, and crushing for later use;
s2: putting the raw materials in the step S1 into a double-screw extruder, respectively carrying out melt blending at the temperature of 155 ℃, 160 ℃, 170 ℃, 180 ℃ and 180 ℃ in each region and at the screw speed of 120rpm, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen of 0.10MPa as a pressure source to form a hollow fiber membrane; spinneret parameters: an inner diameter of 4.0mm and an outer diameter of 4.5mm;
s3: and (3) soaking the hollow fiber membrane in the step (S2) in water at 20 ℃ for 2 hours, washing for 1 hour, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
Example 5
The embodiment provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer containing fluorocarbon chains and polysulfone structures comprises the following steps:
s01: 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine and 4-dimethylaminopyridine are dissolved in dichloromethane and stirred for 18h at room temperature; after the reaction is finished, washing with 1M hydrochloric acid solution for 2 times, washing with deionized water for 2 times, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and vacuum drying at 60 ℃ for 8 hours to obtain an intermediate product I;
the dosage ratio of the 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine, methylene dichloride, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 1mol:1mol:1.4mol:1200mL:1000mL:1000mL:80g;
the dosage of the 4-dimethylaminopyridine is 0.15% of the total mass of the reactants;
intermediate I infrared data are as follows: 3520cm -1 : -OH vanishes; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br is present.
S02: adding o-xylene into a reaction kettle, stirring, introducing nitrogen, adding bisphenol S and sodium hydroxide, heating at 80 ℃ for 2 hours, continuously heating and refluxing until the water discharged from a water separator is constant weight, cooling to room temperature, adding dimethyl sulfoxide and an intermediate product I, heating to 140 ℃ and stirring for 5 hours, cooling to 110 ℃, stopping ventilation, filtering, taking filtrate, respectively washing with 1M hydrochloric acid solution for 2 times, washing with deionized water for 2 times, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, decompressing and distilling the filtrate, and vacuum-drying at 60 ℃ for 8 hours to obtain a target product II;
the dosage ratio of the o-xylene, bisphenol S, sodium hydroxide, dimethyl sulfoxide, intermediate I, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 600mL:0.5mol:1.2mol:500mL:1mol:600mL:600mL:80g;
the infrared data for target product II are as follows: 3520cm -1 : -OH is absent; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br disappeared.
The nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CD 3 CN, δppm): 7.3-8.2 (16H, benzene ring); 4.59 (4H, -CH) 2 -)；
The preparation method of the modified polyvinylidene fluoride water treatment film in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of (1) keeping constant temperature of polyvinylidene fluoride, polyarylene sulfide sulfone, a compatibilizer containing fluorocarbon chains and polysulfone structures, PEG4000 and dimethylacetamide at 60 ℃ for 24 hours, adding the raw materials into a batching kettle according to a proportion, stirring for 10 hours at 150 ℃, cooling a dissolved high polymer solution to room temperature at 200rpm, vacuum drying for 8 hours at 60 ℃, and crushing for later use;
s2: putting the raw materials in the step S1 into a double-screw extruder, respectively carrying out melt blending at 160 ℃ and 160 ℃, 165 ℃, 170 ℃, 180 ℃, 190 ℃ and 190 ℃ in each region and at a screw speed of 140rpm, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen of 0.10MPa as a pressure source to form a hollow fiber membrane; spinneret parameters: an inner diameter of 4.0mm and an outer diameter of 4.5mm;
s3: soaking the hollow fiber membrane in the step S2 in water at 30 ℃ for 2h, washing for 1h, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
Example 6
The embodiment provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer containing fluorocarbon chains and polysulfone structures comprises the following steps:
s01: 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine and 4-dimethylaminopyridine are dissolved in dichloromethane and stirred for 16h at room temperature; after the reaction is finished, washing with 1M hydrochloric acid solution for 2 times, washing with deionized water for 2 times, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure, and vacuum drying at 60 ℃ for 8 hours to obtain an intermediate product I;
the dosage ratio of the 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine, methylene dichloride, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 1mol:1mol:1.4mol:1200mL:1000mL:1000mL:80g;
the dosage of the 4-dimethylaminopyridine is 0.15% of the total mass of the reactants;
intermediate I infrared data are as follows: 3520cm -1 : -OH vanishes; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br is present.
S02: adding o-xylene into a reaction kettle, stirring, introducing nitrogen, adding bisphenol S and sodium hydroxide, heating at 100 ℃ for 3 hours, continuously heating and refluxing until the water discharged from a water separator is constant weight, cooling to room temperature, adding dimethyl sulfoxide and an intermediate product I, heating to 160 ℃ and stirring for 7 hours, cooling to 110 ℃, stopping ventilation, filtering, taking filtrate, respectively washing with 1M hydrochloric acid solution for 2 times, washing deionized water B for 2 times, separating liquid, taking an organic layer, drying with anhydrous sodium sulfate, filtering, decompressing and distilling the filtrate, and vacuum-drying at 60 ℃ for 8 hours to obtain a target product II;
the dosage ratio of the o-xylene, bisphenol S, sodium hydroxide, dimethyl sulfoxide, intermediate I, hydrochloric acid solution, deionized water and anhydrous sodium sulfate is as follows: 600mL:0.5mol:1.2mol:500mL:1mol:600mL:600mL:80g;
the infrared data for target product II are as follows: 3520cm -1 : -OH is absent; 1327cm -1 : -C-F is present; 3020cm -1 、1476cm -1 、1579cm -1 : the benzene ring exists; 1187cm -1 、1362cm -1 : o=s=o present; 884cm -1 : -S-O-present; 684cm -1 : -C-Br disappeared;
the nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CD 3 CN, δppm): 7.3-8.2 (16H, benzene ring); 4.59 (4H, -CH) 2 -)；
The preparation method of the modified polyvinylidene fluoride water treatment film in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of (1) keeping constant temperature of polyvinylidene fluoride, polyarylene sulfide sulfone, a compatibilizer containing fluorocarbon chains and polysulfone structures, PEG6000 and dimethylacetamide for 24 hours at 60 ℃, adding the raw materials into a batching kettle according to a proportion, stirring for 10 hours at 150 ℃, cooling a dissolved high polymer solution to room temperature at 200rpm, vacuum drying for 8 hours at 60 ℃, and crushing for later use;
s2: putting the raw materials in the step S1 into a double-screw extruder, respectively carrying out melt blending at the temperature of 160 ℃, 170 ℃, 180 ℃, 185 ℃ and the screw rotating speed of 150rpm in each region, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen of 0.15MPa as a pressure source to form a hollow fiber membrane; spinneret parameters: an inner diameter of 4.0mm and an outer diameter of 4.5mm;
s3: soaking the hollow fiber membrane in the step S2 in water at 30 ℃ for 2h, washing for 1h, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
The modified polyvinylidene fluoride water treatment films of comparative examples 1 to 8 were all compared with example 1:
comparative example 1
The comparative example provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
a preparation method of a modified polyvinylidene fluoride water treatment film, which comprises the following steps:
s1: the polyvinylidene fluoride, the polyarylene sulfide sulfone, the PEG6000 and the dimethylacetamide are kept at a constant temperature of 60 ℃ for 24 hours, the raw materials are added into a batching kettle according to the proportion, stirred for 10 hours at 150 ℃ and the rotating speed of 200rpm, the dissolved polymer solution is cooled to the room temperature, dried for 8 hours at 60 ℃ in vacuum, and crushed for standby;
s2: putting the raw materials in the step S1 into a double-screw extruder, respectively carrying out melt blending at the temperature of 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ and 130rpm of screw speed in each region, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen of 0.10MPa as a pressure source to form a hollow fiber membrane; spinneret parameters: an inner diameter of 4.0mm and an outer diameter of 4.5mm;
s3: soaking the hollow fiber membrane in the step S2 in water at 50 ℃ for 2h, washing for 1h, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
Comparative example 2
The comparative example provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer with the fluorocarbon chain and polysulfone structure is the same as that of the example 1.
The preparation method of the modified polyvinylidene fluoride water treatment film is the same as that of example 1.
Comparative example 3
The comparative example provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer with the fluorocarbon chain and polysulfone structure is the same as that of the example 1.
The preparation method of the modified polyvinylidene fluoride water treatment film is the same as that of example 1.
Comparative example 4
The comparative example provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer with the fluorocarbon chain and polysulfone structure is the same as that of the example 1.
The preparation method of the modified polyvinylidene fluoride water treatment film is the same as that of example 1.
Comparative example 5
The comparative example provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
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the preparation method of the compatibilizer with the fluorocarbon chain and polysulfone structure is the same as that of the example 1.
The preparation method of the modified polyvinylidene fluoride water treatment film is the same as that of example 1.
Comparative example 6
The comparative example provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer with the fluorocarbon chain and polysulfone structure is the same as that of the example 1.
The preparation method of the modified polyvinylidene fluoride water treatment film is the same as that of example 1.
Comparative example 7
The comparative example provides a modified polyvinylidene fluoride water treatment film, which comprises the following components in parts by weight:
the preparation method of the compatibilizer with the fluorocarbon chain and polysulfone structure is the same as that of the specific example 1.
The preparation method of the modified polyvinylidene fluoride water treatment film comprises the following steps:
s1: keeping the temperature of polyvinylidene fluoride, polyarylene sulfide sulfone, a compatibilizer containing fluorocarbon chains and polysulfone structures and PEG6000 at 60 ℃ for 24 hours for later use;
s2: putting the raw materials in the step S1 into a double-screw extruder, respectively carrying out melt blending at the temperature of 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ and 130rpm of screw speed in each region, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen of 0.10MPa as a pressure source to form a hollow fiber membrane; spinneret parameters: an inner diameter of 4.0mm and an outer diameter of 4.5mm;
s3: soaking the hollow fiber membrane in the step S2 in water at 50 ℃ for 2h, washing for 1h, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
Comparative example 8
A modified polyvinylidene fluoride water treatment film comprises the following raw materials in percentage by weight:
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the preparation method of the compatibilizer with the fluorocarbon chain and polysulfone structure is the same as that of the specific example 1.
The preparation method of the modified polyvinylidene fluoride water treatment film comprises the following steps:
s1: the polyvinylidene fluoride, polyarylene sulfide sulfone, compatibilizer, PEG6000 and dimethylacetamide are added into a batching kettle according to the proportion, stirred for 10 hours at 150 ℃ and the rotating speed is 200rpm, and the dissolved polymer solution is cooled to room temperature and defoamed to obtain casting solution for standby;
s2: pouring the casting solution of the step S1 into a storage tank of a spinning machine, and extruding the casting solution from a spinneret plate to form a hollow fiber membrane by taking high-pressure nitrogen of 0.10MPa as a pressure source; spinneret parameters: an inner diameter of 4.0mm and an outer diameter of 4.5mm;
s3: soaking the hollow fiber membrane in the step S2 in water at 50 ℃ for 2h, washing for 1h, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
Physical properties of the novel modified polyvinylidene fluoride water treatment films prepared in examples 1 to 6 and comparative examples 1 to 8 of the present invention, including pure water flux, rejection rate, porosity, elongation at break, tensile strength, were measured, respectively, and the results are shown in table 1.
Table 1 physical test performance of various examples
From the data in the table, the modified polyvinylidene fluoride water treatment membrane disclosed by the invention not only solves the problem of poor mechanical properties caused by poor compatibility of a polyvinylidene fluoride-polysulfone composite membrane in the prior art by using a self-made compatibilizer, optimizing the formula design and combining the preparation process, but also has obvious advantages in improving the pure water flux, the interception rate and the porosity.
The test method comprises the following steps:
(1) Pure water flux: membrane flux is the volume of solution that passes through a unit of membrane area per unit of time at a certain pressure. The 25cm by 25cm membranes were packed into modules with AB glue and the volume of pure water passing through the membrane modules was measured at 0.1MPa for 1min, and the water flux of the membranes was calculated as follows.
Jw＝V/(A×t)
Wherein the pure water flux of the Jw-film, L/(m) 2 H); v-filtrate volume, L; effective membrane area of A-membrane module, m 2 The method comprises the steps of carrying out a first treatment on the surface of the t-operation time, h.
(2) Rejection rate: the separation performance of the hollow fiber membranes was measured using a bovine serum albumin (BSA, molar mass 67000 g/mol) solution. The permeate was collected by self-preparing a hollow fiber membrane module at room temperature (25 ℃) and a fixed operating pressure (0.1 MPa) from a sample solution of known concentration. Measuring absorbance A of the stock solution with spectrophotometer 2 And absorbance A of the filtrate 1 Calculating the corresponding concentration C of the stock solution BSA according to a standard curve 2 And BSA concentration C of filtrate 1 The retention rate is calculated as follows:
retention = (C 2 －C 1 )/C 2 ×100％。
(3) Porosity: the sample was cut into circles of diameter D and weighed, recorded m 1 The method comprises the steps of carrying out a first treatment on the surface of the Measuring the thickness of the sample by using a micrometer, and recording H; putting the samples into 10mL of water respectively, taking out the samples after 24 hours, wiping off the water on the surfaces, weighing, and recording m 2 。
The porosity calculation formula is as follows:
porosity= (m 2 -m 1 ) V=pi× (D/2) ×100% (ρ×v) ×100%) 2 ×H。
Where ρ is the density of water at normal temperature.
(4) Elongation at break, tensile strength: the test is carried out according to a GB/T1040-2018 plastic stretching test method, and the test speed is 100mm/min.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (9)
1. The modified polyvinylidene fluoride water treatment film is characterized by comprising the following components in parts by weight:
20-30 parts of polyvinylidene fluoride;
5-15 parts of polyarylene sulfide sulfone;
1-3 parts of a compatibilizer containing a fluorocarbon chain and a polysulfone structure;
1.5 parts of PEG;
50.5-72.5 parts of dimethylacetamide;
the compatibilizer with the fluorocarbon chain and polysulfone structure is prepared according to the following method:
s01: 1H, 1H-perfluor nonyl-1-alcohol, 4-bromobenzenesulfonyl chloride, triethylamine and 4-dimethylaminopyridine are dissolved in dichloromethane and stirred for 12 to 20 hours at room temperature; after the reaction is finished, washing with hydrochloric acid solution and deionized water in sequence, separating liquid, taking an organic layer, drying, filtering, distilling filtrate under reduced pressure, and vacuum drying at 60 ℃ for 8 hours to obtain an intermediate product I;
s02: adding o-xylene into a reaction kettle, stirring, introducing nitrogen, adding bisphenol S and sodium hydroxide, heating at 80-100 ℃ for 2-3h, continuously heating and refluxing until the water discharged from a water separator is constant weight, cooling to room temperature, adding dimethyl sulfoxide and an intermediate product I, heating to 140-160 ℃ and stirring for 4-8h, cooling to 110 ℃, stopping introducing nitrogen, filtering, taking filtrate, respectively washing with hydrochloric acid solution and deionized water, separating liquid, taking an organic layer, drying, filtering, decompressing and distilling the filtrate, and vacuum-drying at 60 ℃ for 8h to obtain the compatibilizer with a fluorine-containing carbon chain and polysulfone structure.
2. The modified polyvinylidene fluoride water treatment film according to claim 1, wherein the amount ratio of 1h,1 h-perfluorononyl-1-ol, 4-bromobenzenesulfonyl chloride and triethylamine in step S01 is 1mol:1mol:1.4mol; the dosage of the 4-dimethylaminopyridine is 0.15% of the total mass of the reactants.
3. The modified polyvinylidene fluoride water treatment film according to claim 1, wherein the dosage ratio of o-xylene, bisphenol S, sodium hydroxide, dimethyl sulfoxide, intermediate I in step S02 is 600mL:0.5mol:1.2mol:500mL:1mol.
4. A modified polyvinylidene fluoride water treatment film according to any one of claims 1 to 3, wherein the PEG is PEG4000, PEG6000 or PEG8000.
5. A method for preparing the modified polyvinylidene fluoride water treatment film according to any one of claims 1 to 4, comprising the steps of:
s1: the preparation method comprises the steps of (1) keeping constant temperature for 24 hours at 60 ℃ for polyvinylidene fluoride, polyarylene sulfide sulfone, a compatibilizer containing fluorocarbon chains and polysulfone structures, PEG and dimethylacetamide, adding the raw materials into a batching kettle according to a proportion, stirring for 10 hours at 150 ℃, cooling a dissolved high polymer solution to room temperature at 200rpm, vacuum drying for 8 hours at 60 ℃, and crushing for later use;
s2: putting the crushed raw materials in the step S1 into a double-screw extruder, carrying out melt blending at the temperature of 150-190 ℃ and the rotating speed of 120-150rpm, extruding through a mouth die, sequentially passing through a filter and a spinning pump, and extruding from a spinneret plate by taking high-pressure nitrogen as a pressure source to form a hollow fiber membrane;
s3: and (3) washing the hollow fiber membrane in the step (S2) with water and alcohol, and airing at room temperature to obtain the modified polyvinylidene fluoride water treatment membrane.
6. The method for producing a modified polyvinylidene fluoride water treatment film according to claim 5, wherein the temperature parameters of each zone of the extruder are 150 to 170 ℃, 160 to 180 ℃, 170 to 190 ℃, 180 to 190 ℃ and 180 to 190 ℃.
7. The method for preparing a modified polyvinylidene fluoride water treatment film according to claim 5, wherein the spinneret parameters of the extruder are as follows: an inner diameter of 4.0mm and an outer diameter of 4.5mm; nitrogen pressure: 0.05-0.15MPa.
8. The method for preparing a modified polyvinylidene fluoride water treatment film according to claim 5, wherein the water washing process in step S3 is soaking for 2 hours at 10-50 ℃ and washing for 1 hour.
9. The method for producing a modified polyvinylidene fluoride water treatment film according to claim 5, wherein the alcohol washing in step S3 is carried out at room temperature for 2 hours and for 1 hour.
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