CN113893712B - PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane and preparation method thereof - Google Patents
PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane and a preparation method thereof, and belongs to the technical field of high polymer materials. The method is to synthesize fluorine-containing polyarylethersulfone first, and then the synthesized material and TiO 2 A series of TiO is prepared by a solution blending mode through a dipping precipitation phase inversion film-making process 2 -fluorine-containing polyarylethersulfone ultrafiltration membrane, and finally, compounding with the prepared PVA solution to obtain a compound ultrafiltration membrane; the invention also provides the composite ultrafiltration membrane obtained by the preparation method. The composite ultrafiltration membrane has excellent separation performance, self-cleaning anti-pollution anti-aging and self-repairing capability, greatly prolongs the service life of the ultrafiltration membrane, and has wide application prospect in the technical field of ultrafiltration membrane separation of various water treatments.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane and a preparation method thereof.
Background
The membrane separation technology is a novel efficient separation technology for separating, enriching and purifying a mixture through the selective permeability of a membrane under the pushing of external energy or chemical potential difference. Currently, the technology is one of the best developed emerging technologies. The membrane separation technology has the advantages of simple separation process, low energy consumption, small dosage of medicament, high separation efficiency, convenient operation and the like, so that the membrane separation technology has a huge application prospect in the fields of water treatment, food processing, petrochemical industry and the like. Ultrafiltration is a membrane separation technology taking pressure difference as driving force, has the functions of concentrating, separating and purifying macromolecular substances, and has good interception effect on colloid, protein and other macromolecular substances. At present, various organic polymer materials such as polyethersulfone, polyetherketone, polyacrylonitrile, polyvinylidene fluoride and the like are used for preparing an ultrafiltration membrane, and some materials such as polyaniline, polyphenyl ether and the like are in a research stage. Of these, polyethersulfone (PES) type ultrafiltration membrane materials are the most typical. The material is easy to form a film, has excellent mechanical property, good thermal stability and long service life, and can be suitable for ultrafiltration treatment of various sewage. However, due to the strong hydrophobicity of polyethersulfone, the ultrafiltration membrane is extremely easy to cause membrane pollution in the use process, so that the effective pore diameter of the membrane is reduced or blocked, and the permeation flux and the separation performance of the membrane are obviously reduced, which also becomes a main bottleneck for restricting the development process of the ultrafiltration membrane separation technology in practical application. Aiming at the problems, the performance of the membrane is improved by preparing the composite material, and the prepared composite material can further endow the self-repairing performance on the basis of keeping the excellent self-cleaning performance of the matrix material, so that the method is an effective way for solving the pollution problem of the high polymer ultrafiltration membrane. According to the thought, on one hand, filler with photocatalytic degradation capability is introduced into an ultrafiltration membrane system, so that the active self-cleaning capability of the ultrafiltration membrane is endowed in the separation process; on the other hand, the ultrafiltration membrane is soaked in the hydrogel through physical coating, so that the ultrafiltration membrane is endowed with anti-aging and self-repairing capabilities.
Among various inorganic photocatalysts, tiO 2 The photocatalyst has the advantages of water insolubility, no toxicity, no pollution, low price and higher photocatalytic oxidation activity, and is of great concern. It has now been found that thousands of organic contaminants which are difficult to degrade can pass through TiO under ultraviolet radiation 2 And rapidly degrading. However, under the condition of continuous illumination of the ultrafiltration membrane, aging of the ultrafiltration membrane can be caused, so that the service life of the ultrafiltration membrane is greatly reduced. Therefore, the above problems are solved by introducing a PVA hydrogel having a good self-healing effect. The swelling capacity of PVA hydrogels is the cause of self-repair, and when exposed to water, the hydrogels in the composite expand to fill the damaged area. Meanwhile, the hydrogel and the high polymer material can be tightly combined due to the reversible physical crosslinking effect between the hydrogel and the high polymer material, so that the self-repairing performance of the composite material is endowed. In conclusion, the preparation of the self-repairing reactive ultrafiltration membrane by compounding the hydrogel with the anti-pollution hybrid ultrafiltration membrane has profound significance in the aspects of solving membrane pollution, membrane aging and membrane repair.
Disclosure of Invention
The invention aims to provide a PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane and a preparation method thereof.
The invention firstly provides a preparation method of a PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane, which comprises the following specific steps:
step one: adding hexafluorobisphenol A, fluorine sulfone, salifying agent, reaction solvent and water-carrying agent into a reaction container to react to obtain fluorine-containing polyarylethersulfone polymer matrix material, wherein the structure of the fluorine-containing polyarylethersulfone polymer matrix material is shown as formula I:
in the formula I, n is the polymerization degree, and n=50-500;
step two: the fluorine-containing polyarylethersulfone polymer matrix material prepared in the step one and TiO 2 Dissolving and dispersing the additive in an organic solvent, stirring to prepare a homogeneous casting solution, filtering, standing, degassing, casting the casting solution into a film after complete degassing, evaporating the casting solution in air for 20-40 seconds, immersing the film into deionized water to form a film, and performing post-treatment to obtain x% TiO 2 -fluorine-containing polyarylethersulfone ultrafiltration membranes wherein "x" represents the TiO in the membrane 2 Mass fraction of (a);
step three: mixing polyvinyl alcohol solution with sodium borate decahydrate solution to obtain mixed solution, and then mixing the obtained x% TiO in the second step 2 And placing the fluorine-containing polyarylethersulfone ultrafiltration membrane in the mixed solution for soaking, and cleaning the surface to obtain the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane.
Preferably, the salt forming agent in the step is anhydrous potassium carbonate, the water-carrying agent is toluene, and the reaction solvent is sulfolane.
Preferably, the reaction in the first step is carried out for 2 to 3 hours at 125 to 145 ℃ and then for 6 to 8 hours at 170 to 180 ℃.
Preferably, in the second step, the value range of x is 1-5%.
Preferably, the additive in the second step is polyvinylpyrrolidone.
Preferably, the step two organic solvent is N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) or Tetrahydrofuran (THF).
Preferably, the mass fraction of fluorine-containing polyarylethersulfone in the second casting film solution is 17%.
Preferably, the mass fraction of solute in the step of the polyvinyl alcohol solution is 15%, and the concentration of solute in the sodium borate decahydrate solution is 0.1 mol/liter.
Preferably, the soaking time in the third step is 6-8 hours.
The invention also provides the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane obtained by the preparation method.
The beneficial effects of the invention are that
The invention provides a PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane and a preparation method thereof, wherein the method is to synthesize an anti-aging fluorine-containing polyarylethersulfone, then the synthesized material and a certain proportion of inorganic filler titanium dioxide are subjected to solution blending, a series of titanium dioxide-fluorine-containing polyarylethersulfone ultrafiltration membranes are prepared by using a dipping precipitation phase inversion membrane preparation process, the hydrophilicity of the ultrafiltration membranes is improved by introducing inorganic titanium dioxide particles with photocatalytic activity, and pollutants attached to the ultrafiltration membranes can be degraded, so that the pure water flux of the hybrid ultrafiltration membranes is obviously improved, and the flux of a polyacrylamide solution is slightly improved, so that the separation performance of the prepared titanium dioxide-fluorine-containing polyethersulfone hybrid ultrafiltration membranes is improved. Finally, in order to prevent degradation of contaminants adhering to the ultrafiltration membrane, a small-scale aging effect may be generated on the fluorine-containing polyethersulfone matrix material, resulting in a reduction in the service life of the titanium dioxide-fluorine-containing polyarylethersulfone hybrid ultrafiltration membrane. According to the invention, PVA hydrogel is introduced and compounded with the prepared PVA solution, so that the PVA hydrogel is fully filled in the pore canal of the ultrafiltration membrane, and the PVA hydrogel can be automatically filled at the damaged part of the membrane after the membrane is damaged due to the water absorption and swelling properties of the PVA hydrogel, so that the membrane water flux and the rejection rate are restored to the original level, and the self-repairing property of the composite ultrafiltration membrane is endowed.
The PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane provided by the invention has excellent separation performance, self-cleaning pollution resistance, aging resistance and self-repairing capability, greatly prolongs the service life of the ultrafiltration membrane, and has wide application prospects in the technical field of ultrafiltration membrane separation of various water treatments.
Drawings
FIG. 1 is a graph showing the flux over time for a series of PVA/titania-fluorine-containing polyarylethersulfone self-healing reactive composite ultrafiltration membranes prepared in example 1, example 2, and example 3, in four operating steps.
FIG. 2 shows the total pollution parameters (R) of the series PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in example 1, example 2 and example 3 in a PAM ultrafiltration experiment t ) Reversible pollution parameter (R) r ) And irreversible contamination parameter (R) ir ) Summary of the drawings.
FIG. 3 is a graph showing the water flux recovery efficiency of the series PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in example 1, example 2 and example 3 before and after 30 minutes of simulated sunlight irradiation.
FIG. 4 is a graph showing the retention rate values of the series PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in example 1, example 2 and example 3 before and after 30 minutes of simulated sun light irradiation.
Detailed Description
The invention provides a PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane and a preparation method thereof, and the preparation method specifically comprises the following steps:
step one: the preparation method comprises the steps of mixing hexafluorobisphenol A, fluorine sulfone, a salifying agent, a reaction solvent and a water-carrying agent to obtain a mixture, reacting the mixture at 125-145 ℃ for 2-3 hours preferably, removing water in the water-carrying agent and the reaction process, reacting at 170-180 ℃ for 6-8 hours, washing and drying reactants to obtain the fluorine-containing polyarylethersulfone polymer matrix material.
According to the invention, the salt former is preferably anhydrous potassium carbonate (K 2 CO 3 ) The reaction solvent is preferably sulfolane (TMS), and the water-carrying agent is preferably toluene.
According to the invention, the molar ratio of hexafluorobisphenol A to fluorosulfone is preferably 1:1, a step of; the molar ratio of the fluorine sulfone to the salifying agent is preferably (0.01-0.05): (0.01-0.06); the addition amount of the water-carrying agent is preferably 20-60 milliliters.
According to the invention, the reaction product is washed and dried, preferably in particular: slowly pouring the viscous liquid generated in the reaction vessel into deionized water to obtain a flexible fine strip product, washing the product with the deionized water for 3-5 times, crushing the product into fine granular substances by using a high-speed tissue triturator, boiling and washing the product with deionized water and absolute ethyl alcohol for 3-5 times respectively to remove residual solvents, unreacted monomers and small molecular substances in the crude product, and finally drying the product in a vacuum oven preferably at 60-70 ℃ for 24 hours in vacuum to obtain the fluorine-containing polyether sulfone polymer matrix material. The structure of the compound is shown as formula I:
in the formula I, n is the polymerization degree, and n=50-500;
step two: the fluorine-containing polyarylethersulfone polymer matrix material and TiO obtained in the step one 2 Dissolving an additive, preferably polyvinylpyrrolidone (PVP), in an organic solvent, preferably N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) or Tetrahydrofuran (THF), in an organic solvent, preferably stirring at room temperature for 12-24 hours, preparing a homogeneous casting solution, filtering the obtained casting solution with a filter cloth to remove impurities, preferably standing for 12-24 hours, then placing in a vacuum oven for degassing at 40-60 ℃, casting the casting solution on a glass plate paved with polyester non-woven fabric after complete degassing, scraping the glass plate with a clean film pushing instrument to prepare a film, keeping the casting solution evaporated in the air at room temperature for 20-40 seconds, then immersing in deionized water at 15-25 ℃, and performing post treatment to obtain x% TiO 2 -fluorine-containing polyarylethersulfone ultrafiltration membranes wherein "x" represents the TiO in the membrane 2 Mass fraction of (a); the post-treatment preferably includes: the water bath was changed 6 times within 48 hours, the solvent and the water-soluble polymer additive were completely removed from the film, and the film was then stored in distilled water to be measured.
According to the invention, the fluorine-containing polyarylethersulfone polymer matrix material and TiO 2 And the mass ratio of the additive is preferably 100:1 to 5:10; tiO (titanium dioxide) 2 The mass fraction of the fluorine-containing polyarylethersulfone polymer in the fluorine-containing polyethersulfone hybrid ultrafiltration membrane casting solution is preferably 17%.
According to the invention, the push film thickness value on the scale of the push film instrument is preferably 0.5mm.
Step three: placing polyvinyl alcohol particles in a three-neck flask, adding deionized water, and fully dissolving at 90-95 ℃ to obtain a polyvinyl alcohol solution; dissolving sodium borate decahydrate particles in deionized water at room temperature of 25 ℃ to obtain sodium borate decahydrate solution; mixing the polyvinyl alcohol solution with a sodium borate decahydrate solution to obtain a mixed solution, placing the titanium dioxide-fluorine-containing polyarylethersulfone ultrafiltration membrane obtained in the second step into the prepared mixed solution for full soaking, wherein the soaking time is preferably 6-8 hours, then taking out, and cleaning the surface of the membrane with deionized water to obtain the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane.
According to the invention, the mass fraction of solute in the polyvinyl alcohol solution in the third step is 15%; the concentration of solute in the sodium borate decahydrate solution is 0.1 mole per liter, and the volume ratio of the polyvinyl alcohol solution to the sodium borate decahydrate solution is preferably 17:50.
The composite ultrafiltration membrane disclosed by the invention has better membrane performance, preferably between 1 and 5 percent, and more preferably 5 percent along with the larger adding amount of titanium dioxide, but is not suitable for application because the titanium dioxide is easily lost from the membrane along with the excessive adding amount of the titanium dioxide, so that the content of the titanium dioxide is reasonably controlled.
The invention also provides the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane obtained by the preparation method.
The invention is described in further detail below with reference to the specific examples, wherein the starting materials are commercially available.
Example 1
1) Hexafluorobisphenol a (6.7246 g, 0.020 mol), fluorosulfone (5.0830 g, 0.020 mol), anhydrous potassium carbonate (4.56027 g, 0.021 mol), sulfolane solvent (46 ml) and toluene water-carrying agent (25 ml) were sequentially added to a 100 ml three-neck flask equipped with a mechanical stirrer, a condenser, a water-carrying device, a nitrogen port and a thermometer, the above mixture was stirred at room temperature, then heated to 130 ℃ for reflux reaction for 3 hours, then water-carrying agent toluene and water during the reaction were removed, and the heating was continued to 175 ℃ for reaction for 7 hours, after the polymer became viscous, the polymer was poured into deionized water, boiled and washed 5 times with deionized water and anhydrous ethanol, respectively, to remove the solvent remaining in the crude product and unreacted monomer and small molecular substances, and finally the above product was dried in a vacuum oven at 60 ℃ for 36 hours, to obtain a fluorine-containing polyarylethersulfone material.
2) 0.0194 g of titanium dioxide, 1.938 g of fluorine-containing polyarylethersulfone and 0.193 g of additive polyvinylpyrrolidone (PVP) are dissolved in 20 ml of organic solvent N, N-Dimethylformamide (DMF), stirred for 18 hours to prepare a homogeneous casting solution, impurities are removed by filtering the solution through filter cloth, standing for 12 hours, then placing the solution in a vacuum oven for degassing at 50 ℃, after complete degassing, casting the casting solution on a glass plate paved with polyester non-woven fabrics, scraping the glass plate into a film by using a clean scraper, keeping the casting solution evaporated in air for 30 seconds at room temperature of 25 ℃, and then immersing the solution in deionized water to form the film. Thereafter, the water bath was changed 6 times within 48 hours, and the solvent and the water-soluble polymer additive were completely removed from the film, after which the film was kept in distilled water for use. The hybrid membrane prepared was named 1% TiO 2 -fluorine-containing polyarylethersulfones, wherein "x" represents the TiO in the hybrid film 2 Mass fraction of (c) is determined.
3) 6 g of polyvinyl alcohol particles are added into a 100 ml round bottom three-neck flask, 34 ml of deionized water is added, and the mixture is heated and stirred for 4 hours at 95 ℃ to obtain a polyvinyl alcohol solution with the mass fraction of 15%, and then the polyvinyl alcohol solution is poured into a culture dish for standby. 3.81 g of sodium borate decahydrate was added to a 200 ml beaker, and 100 ml of deionized water was added, and after complete dissolution, poured into a polyvinyl alcohol solution to form a mixed solution. Soaking the 1% titanium dioxide-fluorine-containing polyarylethersulfone ultrafiltration membrane prepared in the step 2) in the mixed solution for 7 hours, taking out and cleaning the surface of the membrane by deionized water to obtain the PVA/1% titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane.
Example 2
1) The fluorine-containing polyarylethersulfone material was prepared as described in 1) of example 1.
2) 0.0581 g of titanium dioxide, 1.938 g of fluoropolyether sulfone and 0.193 g of polyvinylpyrrolidone (PVP) as additive were dissolved in 20 ml of organic solvent N, N-Dimethylformamide (DMF) and stirred for 18 hours to prepare a homogeneous casting solution. The solution was then filtered using a filter cloth to remove impurities, left to stand for 12 hours and then placed in a vacuum oven for degassing at 50 ℃. After degassing was completed, the casting solution was cast on a glass plate laid with a polyester nonwoven fabric, scraped into a film with a clean doctor blade, kept evaporated in air at room temperature of 25 ℃ for 30 seconds, and then immersed in deionized water to form a film. Thereafter, the water bath was changed 6 times within 48 hours, and the solvent and the water-soluble polymer additive were completely removed from the film, after which the film was kept in distilled water for use. The hybrid membrane prepared was designated 3% titania-fluoropolyether sulfone, where "x" represents the mass fraction of titania in the hybrid membrane.
3) 6 g of polyvinyl alcohol particles are added into a 100 ml round bottom three-neck flask, 34 ml of deionized water is added, and the mixture is heated and stirred for 4 hours at 95 ℃ to obtain a polyvinyl alcohol solution with the mass fraction of 15%, and then the polyvinyl alcohol solution is poured into a culture dish for standby. 3.81 g of sodium borate decahydrate was added to a 200 ml beaker, and 100 ml of deionized water was added, and after complete dissolution, poured into a polyvinyl alcohol solution to form a mixed solution. Soaking the 3% titanium dioxide-fluorine-containing polyarylethersulfone ultrafiltration membrane prepared in the step 2) in the mixed solution for 7 hours, taking out and cleaning the surface of the membrane with deionized water, and finally obtaining the PVA/3% titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane.
Example 3
1) The fluorine-containing polyarylethersulfone material was prepared as described in 1) of example 1.
2) 0.0969 g of titanium dioxide, 1.938 g of fluoropolyether sulfone and 0.193 g of polyvinylpyrrolidone (PVP) as additive were dissolved in 20 ml of organic solvent N, N-Dimethylformamide (DMF) and stirred for 12 hours to prepare a homogeneous casting solution. The solution was then filtered using a filter cloth to remove impurities, left to stand for 12 hours and then placed in a vacuum oven for degassing at 50 ℃. After degassing was completed, the casting solution was cast on a glass plate laid with a polyester nonwoven fabric, scraped into a film with a clean doctor blade, kept evaporated in air at room temperature of 25 ℃ for 30 seconds, and then immersed in deionized water to form a film. Thereafter, the water bath was changed 6 times within 48 hours, and the solvent and the water-soluble polymer additive were completely removed from the film, after which the film was kept in distilled water for use. The hybrid membrane prepared was designated as 5% titania-fluoropolyether sulfone, where "x" represents the mass fraction of titania in the hybrid membrane.
3) 6 g of polyvinyl alcohol particles are added into a 100 ml round bottom three-neck flask, 34 ml of deionized water is added, and the mixture is heated and stirred for 4 hours at 95 ℃ to obtain a polyvinyl alcohol solution with the mass fraction of 15%, and then the polyvinyl alcohol solution is poured into a culture dish for standby. 3.81 g of sodium borate decahydrate was added to a 200 ml beaker, and 100 ml of deionized water was added, and after complete dissolution, poured into a polyvinyl alcohol solution to form a mixed solution. Soaking the 5% titanium dioxide-fluorine-containing polyarylethersulfone ultrafiltration membrane prepared in the step 2) in the mixed solution for 7 hours, taking out and cleaning the surface of the membrane with deionized water, and finally obtaining the PVA/5% titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane.
FIG. 1 shows the flux change with time in four operating steps of the series PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-healing reactive composite ultrafiltration membranes prepared in example 1, example 2 and example 3 described above. The four operation steps are respectively as follows: the membrane was tested for 15 minutes pure water flux, 30 minutes Polyacrylamide (PAM) solution flux, 30 minutes pure water flux after hydraulic cleaning, 30 minutes pure water flux after simulated solar light irradiation, 30 minutes pure water flux after 30 minutes.
Fig. 1 illustrates: in the content range of titanium dioxide, the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane increases with the increase of the titanium dioxide content, and the pure water flux is increased along with the increase of the titanium dioxide content, so that the hydrophilicity of the ultrafiltration membrane is further improved. In addition, the ultrafiltration membrane has low flux on the polyacrylamide solution, because the polyacrylamide pollutes the ultrafiltration membrane. After the ultrafiltration membrane is subjected to hydraulic cleaning, the pure water flux of the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane still becomes larger along with the increase of the titanium dioxide content, and the introduction of the titanium dioxide increases the hydrophilicity of the ultrafiltration membrane, so that pollutants are easier to remove in the hydraulic cleaning process, and the anti-pollution performance of the ultrafiltration membrane is obviously improved. In addition, as can be found from the data in fig. 1, the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane is remarkably improved in pure water flux after being irradiated by simulated solar light, because the inorganic titanium dioxide nanoparticles can degrade part of pollutants attached to the ultrafiltration membrane through photocatalytic oxidation, thereby endowing the hybrid ultrafiltration membrane with certain self-cleaning capability and further enhancing the anti-pollution capability.
FIG. 2 shows the total pollution parameters (R) of the series PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in the above example 1, example 2 and example 3 in the PAM ultrafiltration experiment t ) Reversible pollution parameter (R) r ) And irreversible contamination parameter (R) ir ) Summary of the drawings. As can be seen from the analysis of the data in FIG. 2, the total pollution coefficient of the ultrafiltration membrane is larger and reaches more than 90% in the process of testing the pollution resistance of the ultrafiltration membrane, which is mainly caused by the larger pure water flux of the ultrafiltration membrane. However, as the content of titanium dioxide is increased, the reversible pollution parameters of the ultrafiltration membrane are gradually increased, and the irreversible pollution parameters are gradually reduced, because the introduction of titanium dioxide with different contents gradually increases the hydrophilicity of the ultrafiltration membrane, the proportion of the reversible pollution in the total pollution is increased, and the anti-pollution performance of the ultrafiltration membrane is obviously improved.
FIG. 3 shows the water flux recovery efficiency of the series PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in the above examples 1, 2 and 3 before and after 30min of simulated sunlight irradiation. As can be seen from the data in fig. 3, the flux recovery efficiency increases significantly as the titanium dioxide content of the ultrafiltration membrane increases. The inorganic titanium dioxide particles in the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane can degrade part of pollutants attached to the ultrafiltration membrane through photocatalytic oxidation after being irradiated by simulated sunlight, so that the hybridization ultrafiltration membrane has certain self-cleaning capability.
FIG. 4 shows the retention rate values of the series PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in the above examples 1, 2 and 3 before and after 30min of simulated sun light. The graph shows that the retention rate of the composite ultrafiltration membranes with different titanium dioxide contents is almost unchanged, which indicates that PVA endows the ultrafiltration membranes with self-repairing performance.
Claims (10)
1. A preparation method of a PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane is characterized by comprising the following specific steps:
step one: adding hexafluorobisphenol A, fluorine sulfone, salifying agent, reaction solvent and water-carrying agent into a reaction container to react to obtain fluorine-containing polyarylethersulfone polymer matrix material, wherein the structure of the fluorine-containing polyarylethersulfone polymer matrix material is shown as formula I:
in the formula I, n is the polymerization degree, and n=50-500;
step two: the fluorine-containing polyarylethersulfone polymer matrix material prepared in the step one and TiO 2 Dissolving and dispersing the additive in an organic solvent, stirring to prepare a homogeneous casting solution, filtering, standing, degassing, casting the casting solution into a film after complete degassing, evaporating the casting solution in air for 20-40 seconds, immersing the film into deionized water to form a film, and performing post-treatment to obtain x% TiO 2 -fluorine-containing polyarylethersulfone ultrafiltration membranes wherein x represents TiO in the membrane 2 Mass fraction of (a);
step three: mixing polyvinyl alcohol solution with sodium borate decahydrate solution to obtain mixed solution, and then mixing the obtained x% TiO in the second step 2 And placing the fluorine-containing polyarylethersulfone ultrafiltration membrane in the mixed solution for soaking, and cleaning the surface to obtain the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane.
2. The method for preparing the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein the salt forming agent is anhydrous potassium carbonate, the water-carrying agent is toluene, and the reaction solvent is sulfolane.
3. The method for preparing the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein the reaction in the first step is carried out for 2-3 hours at 125-145 ℃ and then for 6-8 hours at 170-180 ℃.
4. The method for preparing the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein the value range of x in the second step is 1-5%.
5. The method for preparing the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein the additive in the second step is polyvinylpyrrolidone.
6. The method for preparing the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein the second organic solvent is N, N-dimethylformamide, N-dimethylacetamide or tetrahydrofuran.
7. The method for preparing the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein the mass fraction of fluorine-containing polyarylethersulfone in the second casting solution is 17%.
8. The method for preparing a PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein the mass fraction of the solute in the polyvinyl alcohol solution in the step is 15%, and the concentration of the solute in the sodium borate decahydrate solution is 0.1 mol/liter.
9. The method for preparing the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein the soaking time in the third step is 6-8 hours.
10. The PVA/titania-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane obtained by the preparation method of claim 1.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1683061A (en) * | 2005-03-08 | 2005-10-19 | 中国人民解放军军事医学科学院卫生装备研究所 | Nano antiseptic material-polysulphone composite microporous filter film and its preparing method |
| CN1978036A (en) * | 2005-12-06 | 2007-06-13 | 浙江工商大学 | Method for preparing polyuinyl alcohol/polyamide |
| CN101785976A (en) * | 2009-11-13 | 2010-07-28 | 山东东岳高分子材料有限公司 | Polymer separation membrane with on-line antibiosis and self-cleaning functions and preparation method thereof |
| CN104258745A (en) * | 2014-10-24 | 2015-01-07 | 南京水思环保科技有限公司 | Preparation method of hydrophilic polyethersulfone microfiltration membrane |
| KR20150068216A (en) * | 2013-12-11 | 2015-06-19 | 한국화학연구원 | A PVA coated hollow fiber mambrane and a preparation method thereof |
| CN105694458A (en) * | 2016-04-11 | 2016-06-22 | 东北师范大学 | TiO2/fluorine-containing polyether sulphone, preparation method and hybrid ultrafiltration membrane |
| CN106914154A (en) * | 2017-02-27 | 2017-07-04 | 武汉科技大学 | PEG‑TiO2The preparation method of the hydrophilic milipore filters of/PES/PVA and application |
| CN109603589A (en) * | 2019-01-04 | 2019-04-12 | 东北师范大学 | A kind of Ag@NH2- MIL-125/ polyether sulphone hydridization dense form reactivity ultrafiltration membrane and preparation method thereof |
| WO2019137054A1 (en) * | 2018-01-09 | 2019-07-18 | 时代沃顿科技有限公司 | Preparation method for super-hydrophilic ultrafiltration membrane having photocatalytic properties |
| CN110559883A (en) * | 2019-09-04 | 2019-12-13 | 东北师范大学 | PVA/boric acid group-containing polyether sulfone self-healing composite ultrafiltration membrane and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8110639B2 (en) * | 2006-11-17 | 2012-02-07 | Solvay Advanced Polymers, L.L.C. | Transparent and flame retardant polysulfone compositions |
| US7977451B2 (en) * | 2006-12-15 | 2011-07-12 | General Electric Company | Polyarylether membranes |
-
2021
- 2021-10-26 CN CN202111245523.9A patent/CN113893712B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1683061A (en) * | 2005-03-08 | 2005-10-19 | 中国人民解放军军事医学科学院卫生装备研究所 | Nano antiseptic material-polysulphone composite microporous filter film and its preparing method |
| CN1978036A (en) * | 2005-12-06 | 2007-06-13 | 浙江工商大学 | Method for preparing polyuinyl alcohol/polyamide |
| CN101785976A (en) * | 2009-11-13 | 2010-07-28 | 山东东岳高分子材料有限公司 | Polymer separation membrane with on-line antibiosis and self-cleaning functions and preparation method thereof |
| KR20150068216A (en) * | 2013-12-11 | 2015-06-19 | 한국화학연구원 | A PVA coated hollow fiber mambrane and a preparation method thereof |
| CN104258745A (en) * | 2014-10-24 | 2015-01-07 | 南京水思环保科技有限公司 | Preparation method of hydrophilic polyethersulfone microfiltration membrane |
| CN105694458A (en) * | 2016-04-11 | 2016-06-22 | 东北师范大学 | TiO2/fluorine-containing polyether sulphone, preparation method and hybrid ultrafiltration membrane |
| CN106914154A (en) * | 2017-02-27 | 2017-07-04 | 武汉科技大学 | PEG‑TiO2The preparation method of the hydrophilic milipore filters of/PES/PVA and application |
| WO2019137054A1 (en) * | 2018-01-09 | 2019-07-18 | 时代沃顿科技有限公司 | Preparation method for super-hydrophilic ultrafiltration membrane having photocatalytic properties |
| CN109603589A (en) * | 2019-01-04 | 2019-04-12 | 东北师范大学 | A kind of Ag@NH2- MIL-125/ polyether sulphone hydridization dense form reactivity ultrafiltration membrane and preparation method thereof |
| CN110559883A (en) * | 2019-09-04 | 2019-12-13 | 东北师范大学 | PVA/boric acid group-containing polyether sulfone self-healing composite ultrafiltration membrane and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Poly (vinyl alcohol) (PVA) hydrogel incorporated with Ag/TiO2 for rapid sterilization by photoinspired radical oxygen species and promotion of wound healing;Wang, JM et.al;APPLIED SURFACE SCIENCE;第494卷;第708-720页 * |
| Transport, structural, and interfacial properties of poly (vinyl alcohol)-polysulfone composite nanofiltration membranes;Peng, FB et.al;JOURNAL OF MEMBRANE SCIENCE;第353卷(第1-2期);第169-176页 * |
| 自支撑NH_2-MIL-125/聚■二唑复合正渗透膜的制备及性能;何男;刘威;杨霞;王宪泽;崔晓春;吴敬慧;耿直;;高等学校化学学报(06);第254-261页 * |
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