CN113975982B - Preparation method of polyvinylidene fluoride composite film - Google Patents
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- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 88
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005266 casting Methods 0.000 claims abstract description 23
- 239000011521 glass Substances 0.000 claims abstract description 16
- 238000005191 phase separation Methods 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000007790 scraping Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 229920002490 poly(thioether-sulfone) polymer Polymers 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims description 6
- -1 phosphorus sulfone Chemical class 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 5
- 229920006295 polythiol Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229920001021 polysulfide Polymers 0.000 claims 1
- 239000005077 polysulfide Substances 0.000 claims 1
- 150000008117 polysulfides Polymers 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 230000004907 flux Effects 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000000108 ultra-filtration Methods 0.000 abstract description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 10
- 229940098773 bovine serum albumin Drugs 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229960000502 poloxamer Drugs 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a preparation method of a polyvinylidene fluoride composite film, which comprises the following steps: step S1: preparing a modified PVDF casting solution, adding sPSSPO, nano ZnO, PVP, F127 and PVDF into N, N-dimethylacetamide, stirring at a preset temperature, standing and defoaming to obtain the modified PVDF casting solution; step S2: preparing a PVDF modified film, uniformly scraping the modified PVDF casting film liquid on a glass plate, and then placing the glass plate coated with the modified PVDF casting film liquid into a gel bath for phase separation to obtain the PVDF modified film. Compared with the traditional PVDF ultrafiltration membrane, the invention can obviously improve the hydrophilicity of the PVDF membrane, enhance the water flux and BSA interception rate of the PVDF membrane, enhance the adsorption capacity of the PVDF membrane on pollutants in wastewater, and has excellent visible light photocatalysis performance.
Description
Technical Field
The invention relates to membrane separation and photocatalysis technologies, in particular to a preparation method of a polyvinylidene fluoride composite membrane.
Background
The photocatalysis technology is a novel advanced oxidation technology, and can decompose most organic and inorganic substances under the illumination condition. Compared with ultraviolet light harmful to the body, the sunlight is more environment-friendly and can avoid resource waste. ZnO is used as a common photocatalyst and has good photocatalytic activity in a sunlight wave band, and meanwhile, the ZnO has the advantages of low price, no toxicity, strong photochemical stability and the like, so that the ZnO is widely applied to the field of sewage treatment. However, znO nano particles are difficult to separate and recycle in the photocatalytic reaction, so that the large-scale production application and the further development of the ZnO nano particles are seriously influenced.
The membrane separation technology has the advantages of low energy consumption, no secondary pollution, convenient operation, simple equipment, no phase change, high separation speed and the like compared with the traditional separation technology due to the physical separation characteristic, and is widely applied to the treatment and reuse of various sewage and wastewater. Among the numerous membrane materials of membrane separation technology, polyvinylidene fluoride (PVDF) has been attracting attention and not broken innovations in membrane separation technology due to its excellent thermal stability, aging resistance and chemical stability. However, PVDF membranes have a strong hydrophobicity, which in turn affects operating efficiency and increases costs during application. Therefore, researchers have been devoted to hydrophilizing and modifying them by a certain means, thereby improving the membrane adsorption performance and catalytic performance. The Wu Q takes F127 as a modifier to prepare a PVDF/F127 composite membrane, and the hydrophilicity and permeability of the PVDF/F127 composite membrane are improved (Wu Q.CHEMICAL ENGINEERING JOURNAL-LAUSANNE-, 2017.). Chen Z added PVP to the PVDF membrane, the pore size structure was evident, but the hydrophilicity was not significantly improved. To overcome the above drawbacks, new modifiers are being sought for improving the hydrophilicity of PVDF (Chen Z. Separation and Purification Technology,2020, 259:118184.).
The sulfonated polythioether sulfone phosphine oxide has excellent water resistance, heat resistance and film forming property, and has wide application in the fields of ion exchange resin, film separation, sensors and the like. Sulfonated polythioether sulfone crosslinking membrane disclosed in China patent (issued publication number: CN 101024701A) and preparation method thereof. The sulfonated polythioether sulfone membrane prepared by adopting the phase inversion method has high swelling degree and good hydrophilicity. Chinese patent (publication No. CN 108172876A) discloses a polythioether oxygen phosphorus proton exchange membrane which has strong water absorption and moisture retention property and cohesiveness with inorganic or polymer materials due to the triphenyl oxygen phosphorus group contained in the membrane, shows excellent performance and has potential application value in the field of membrane separation.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a sulfonated polythioether sulfone phosphine oxide zinc oxide polyvinylidene fluoride composite membrane, which can not only remarkably improve the hydrophilicity of the PVDF membrane and enhance the water flux and BSA retention rate of the PVDF membrane, but also enhance the adsorption capacity of the PVDF membrane to pollutants in wastewater, and the prepared composite PVDF membrane has excellent visible light photocatalytic performance.
The preparation method of the polyvinylidene fluoride composite film provided by the invention comprises the following steps:
step S1: preparing a modified PVDF casting solution, adding sPSSPO, nano ZnO, PVP, F127 and PVDF into N, N-dimethylacetamide, stirring at a preset temperature, standing and defoaming to obtain the modified PVDF casting solution;
step S2: preparing a PVDF modified film, uniformly scraping the modified PVDF casting film liquid on a glass plate, and then placing the glass plate coated with the modified PVDF casting film liquid into a gel bath for phase separation to obtain the PVDF modified film.
Preferably, in step S1, the mass ratio of sPSSPO, znO, PVP, F to PVDF is (0-0.3): 1:0.8:0.8:8;
the total mass fraction of sPSSPO, PVP, F and PVDF in the modified PVDF film casting solution is 19.2-19.8%.
Preferably, the sPSSPO is monosulfonated polythioether sulfone oxygen.
Preferably, in step S1, the preset temperature is 40-70 ℃, and the stirring time is 8-16 h.
Preferably, in step S2, the doctor blade thickness of the modified PVDF casting solution on the glass plate is 100 to 250 μm.
Preferably, in step S2, deionized water is used for the gel bath, and the temperature of the gel bath is 15-30 ℃.
Preferably, in step S2, the PVDF modified film is immersed in deionized water for 4 to 7 days to remove the excess solvent and pore-forming agent, and then put into clean deionized water for preservation.
Preferably, said sPSSPO acts as a hydrophilic modifier; the ZnO is used as a photocatalytic active center; the PVP is used as a pore-forming agent.
The test shows that the pure water flux of the modified PVDF film prepared by the invention is up to 169.2 L.m -2·h-1, the retention rate of Bovine Serum Albumin (BSA) is 64.35%, and the conversion rate of photocatalytic degradation of Methylene Blue (MB) can be up to 98.68%;
The modified PVDF composite membrane in the invention shows excellent adsorptivity and photocatalytic performance when being treated with Methylene Blue (MB) solution, and the adsorption rate is obviously improved. This is because after adding monosulfonated polythioether sulfone phosphorus oxide, the triphenyl phosphorus oxide group has strong hydrophilicity, so that the adsorption performance is obviously improved. On the other hand, the addition of the monosulfonated polythioether sulfone oxygen phosphorus enhances the cohesiveness of inorganic matters and polymer materials, so that inorganic nano particles embedded into the surface of the modified film are not easy to fall off, and the photocatalytic performance is improved.
The modified PVDF composite membrane of the invention has better pollution resistance and obviously improved retention rate when being treated with Bovine Serum Albumin (BSA) solution. This is because the more hydrophilic the film is, the better the anti-fouling properties are. Meanwhile, the pore diameter structure of the modified membrane is smaller than that of the BSA molecules, so that the BSA molecules can be effectively intercepted, and the higher rejection rate is shown.
The preparation method of the invention adopts a blending method to add the hydrophilic modifier, the photocatalyst, the pore-forming agent and the like into PVDF to obtain modified casting film liquid, and then adopts a non-solvent induced phase separation method to obtain the modified PVDF composite film, so that the hydrophilicity of the composite film is greatly improved, the pollution resistance and the interception performance of the composite film are obviously improved, and the composite film also has better photocatalytic performance. Compared with other methods, the blending modification and film forming process is simple, and complex post-treatment steps are not needed.
Compared with the prior art, the invention has the following beneficial effects:
Compared with the traditional PVDF ultrafiltration membrane, the invention can obviously improve the hydrophilicity of the PVDF membrane, enhance the water flux and BSA interception rate of the PVDF membrane, enhance the adsorption capacity of the PVDF membrane on pollutants in wastewater, and has excellent visible light photocatalysis performance.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a flow chart showing the steps of a method for preparing a polyvinylidene fluoride composite film according to an embodiment of the present invention;
FIG. 2 is a graph showing the comparison of water flux and rejection of modified membranes in examples 1-3 and comparative examples of the present invention;
FIG. 3 is a graph comparing catalytic efficiencies of modified membranes in examples 1-3 of the present invention with those of comparative examples.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Comparative example:
The embodiment is to directly prepare a ZnO-based PVDF modified composite membrane without sPSSPO by using NIPS (non-solvent induced phase separation method, nonsolvent Induce Phase Separation), and the specific preparation method is as follows:
(1) Adding nano ZnO, F127, PVP and PVDF into a DMAc solvent, wherein the components are as follows: f127: PVP: PVDF=1:0.8:0.8:8, stirring at 70 ℃ for 10 hours to fully dissolve (disperse), and standing and defoaming for 24 hours to obtain a casting solution;
(2) Scraping the casting solution obtained in the step (1) on a glass plate to form a film with the thickness of 250 mu m;
(3) Immersing the glass plate with the membrane liquid in the step (2) into deionized water gel bath at 25 ℃ for phase separation;
(4) Transferring the membrane subjected to phase separation in the step (3) into deionized water, soaking for 7 days to remove redundant solvent and pore-forming agent, and then placing the membrane into clean deionized water for preservation to obtain a PVDF modified composite membrane, namely an M0 modified membrane.
Example 1:
The embodiment is to directly prepare a sulfonated polythioether sulfone phosphine oxide-zinc oxide/polyvinylidene fluoride composite membrane by using an NIPS method, and the specific preparation method is as follows:
(1) sPSSPO, znO, F127, PVP and PVDF are added into DMAc solvent, and the components are mixed according to the proportion of sPSSPO: znO: f127: PVP: pvdf=0.1:1:0.8:0.8:8, and after stirring at 70 ℃ for 10 hours to sufficiently dissolve (disperse), standing and defoaming for 24 hours;
(2) Scraping the casting solution obtained in the step (1) on a glass plate to form a film with the thickness of 250 mu m;
(3) Immersing the glass plate with the membrane liquid in the step (2) into deionized water gel bath at 25 ℃ for phase separation;
(4) Transferring the membrane subjected to phase separation in the step (3) into deionized water, soaking for 7 days to remove redundant solvent and pore-forming agent, and then placing the membrane into clean deionized water for preservation to obtain a PVDF modified composite membrane, which is marked as an M1 modified membrane.
SPSSPO is monosulfonated polythioether sulfone oxygen; the F127 is poloxamer; the PVP is polyvinylpyrrolidone; the PVDF is polyvinylidene fluoride; the DMAc is N, N-dimethylacetamide.
Example 2:
The embodiment is to directly prepare a sulfonated polythioether sulfone phosphine oxide-zinc oxide/polyvinylidene fluoride composite membrane by using an NIPS method, and the specific preparation method is as follows:
(1) sPSSPO, znO, F127, PVP and PVDF are added into DMAc solvent, and the components are mixed according to the proportion of sPSSPO: znO: f127: PVP: pvdf=0.2:1:0.8:0.8:8, and after stirring at 70 ℃ for 10 hours to sufficiently dissolve (disperse), standing and defoaming for 24 hours;
(2) Scraping the casting solution obtained in the step (1) on a glass plate to form a film with the thickness of 250 mu m;
(3) Immersing the glass plate with the membrane liquid in the step (2) into deionized water gel bath at 25 ℃ for phase separation;
(4) Transferring the membrane subjected to phase separation in the step (3) into deionized water, soaking for 7 days to remove redundant solvent and pore-forming agent, and then placing the membrane into clean deionized water for preservation to obtain a PVDF modified composite membrane, namely an M2 modified membrane.
Example 3:
The embodiment is to directly prepare a sulfonated polythioether sulfone phosphine oxide-zinc oxide/polyvinylidene fluoride composite membrane by using an NIPS method, and the specific preparation method is as follows:
(1) sPSSPO, znO, F127, PVP and PVDF are added into DMAc solvent, and the components are mixed according to the proportion of sPSSPO: znO: f127: PVP: pvdf=0.3:1:0.8:0.8:8, and after stirring at 70 ℃ for 10 hours to sufficiently dissolve (disperse), standing and defoaming for 24 hours;
(2) Scraping the casting solution obtained in the step (1) on a glass plate to form a film with the thickness of 250 mu m;
(3) Immersing the glass plate with the membrane liquid in the step (2) into deionized water gel bath at 25 ℃ for phase separation;
(4) Transferring the membrane subjected to phase separation in the step (3) into deionized water, soaking for 7 days to remove redundant solvent and pore-forming agent, and then placing the membrane into clean deionized water for preservation to obtain a PVDF modified composite membrane, namely an M3 modified membrane.
Performance testing of various composite films:
The modified films of examples 1 to 3 and comparative examples were subjected to permeation performance and photocatalytic performance test.
The pure water flux is 1g/L in the permeability test process, and the retention rate data of the BSA solution are collected by a cross-flow filter device under 0.1 MPa; data were collected after 30min pre-pressing each membrane with DI water to ensure accuracy. The data in FIG. 1 are stable values obtained by measuring three or more sheets for each of the films of examples 1 to 3 and comparative examples. As can be seen from fig. 1, the films of M1, M2, M3, etc. added with sPSSPO all exhibited excellent water permeability and BSA retention properties as compared to the M0 composite film without sPSSPO.
Photocatalytic performance the photocatalytic degradation test was carried out with an MB aqueous solution at room temperature of 25℃and the initial volume of the solution was 90.0ml and the initial concentration C 0 was 10.0 mg.l -1. After adsorption for 120min in dark condition reached adsorption equilibrium, the suspension was irradiated for 160min under visible light provided by a 250W light power xenon lamp. The residual MB concentration was measured using an ultraviolet-visible spectrophotometer, C t being the concentration of MB in the solution at time t. The test results are shown in figure 2. As can be seen from fig. 2, the hydrophilicity of the modified film is enhanced with an increase in the addition amount of the sulfonated polymer under dark conditions, and the adsorption performance thereof is significantly improved. After 120min of adsorption, the modified PVDF film has excellent effect of catalyzing and degrading MB under visible light, and when the mass ratio of components of the casting film liquid is sPSSPO: znO: f127: PVP: pvdf=0.2:1:0.8:0.8:8, photocatalytic degradation efficiency is as high as 98.68%.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (6)
1. The preparation method of the polyvinylidene fluoride composite film is characterized by comprising the following steps of:
step S1: preparing a modified PVDF casting solution, adding monosulfonated polythioether phosphorus sulfone, nano ZnO, PVP, F and PVDF into N, N-dimethylacetamide, stirring at a preset temperature, standing and defoaming to obtain the modified PVDF casting solution;
Step S2: preparing a PVDF modified membrane, uniformly scraping the modified PVDF casting solution on a glass plate, and then placing the glass plate coated with the modified PVDF casting solution into a gel bath for phase separation to obtain the PVDF modified membrane;
In the step S1, the mass ratio of the monosulfonated polythioether sulfone oxygen phosphorus, znO, PVP, F127,127 and PVDF is (0.1-0.3) 1:0.8:0.8:8;
the total mass fraction of the monosulfonated polythioether sulfone oxygen phosphorus, PVP, F127 and PVDF in the modified PVDF film casting solution is 19.2-19.8%.
2. The method for producing a polyvinylidene fluoride composite film according to claim 1, wherein in step S1, the preset temperature is 40 to 70 ℃ and the stirring time is 8 to 16 hours.
3. The method for producing a polyvinylidene fluoride composite film according to claim 1, wherein in step S2, the doctor blade thickness of the modified PVDF casting solution on the glass sheet is 100 to 250 μm.
4. The method for preparing a polyvinylidene fluoride composite film according to claim 1, wherein deionized water is used for the gel bath in step S2, and the temperature of the gel bath is 15-30 ℃.
5. The method for preparing a polyvinylidene fluoride composite membrane according to claim 1, wherein in step S2, the PVDF modified membrane is immersed in deionized water for 4 to 7 days to remove excess solvent and pore-forming agent, and then stored in clean deionized water.
6. The method for preparing a polyvinylidene fluoride composite membrane according to claim 1, wherein the monosulfonated polysulfide sulfone oxygen phosphorus is used as a hydrophilic modifier; the ZnO is used as a photocatalytic active center; the PVP is used as a pore-forming agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111281240.XA CN113975982B (en) | 2021-11-01 | 2021-11-01 | Preparation method of polyvinylidene fluoride composite film |
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| EP0671466A1 (en) * | 1994-03-08 | 1995-09-13 | Tech-Sep | Microfiltration of beer |
| CN101024701A (en) * | 2007-02-13 | 2007-08-29 | 上海氯碱化工股份有限公司 | Sulfonated polysulfide-ether-sulfone crosslinking film and preparing method |
| WO2010120859A1 (en) * | 2009-04-17 | 2010-10-21 | Arkema Inc. | Blends of polyvinylidene fluoride copolymers with sulfonated poly(ether sulfones) |
| CN103506016A (en) * | 2012-06-29 | 2014-01-15 | 南京理工大学 | Novel sulfonated polyarylether sulfone water treatment ultrafiltration membrane and preparation method thereof |
| CN109012229A (en) * | 2018-09-03 | 2018-12-18 | 华南理工大学 | A kind of high throughput PVDF ultrafiltration membrane and the preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0671466A1 (en) * | 1994-03-08 | 1995-09-13 | Tech-Sep | Microfiltration of beer |
| CN101024701A (en) * | 2007-02-13 | 2007-08-29 | 上海氯碱化工股份有限公司 | Sulfonated polysulfide-ether-sulfone crosslinking film and preparing method |
| WO2010120859A1 (en) * | 2009-04-17 | 2010-10-21 | Arkema Inc. | Blends of polyvinylidene fluoride copolymers with sulfonated poly(ether sulfones) |
| CN103506016A (en) * | 2012-06-29 | 2014-01-15 | 南京理工大学 | Novel sulfonated polyarylether sulfone water treatment ultrafiltration membrane and preparation method thereof |
| CN109012229A (en) * | 2018-09-03 | 2018-12-18 | 华南理工大学 | A kind of high throughput PVDF ultrafiltration membrane and the preparation method and application thereof |
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