CN113893712A - PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane and preparation method thereof - Google Patents
PVA/titanium dioxide-fluorine-containing polyarylether sulfone 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 polyarylether sulfone self-repairing reactive composite ultrafiltration membrane and a preparation method thereof, belonging to the technical field of high polymer materials. Firstly synthesizing fluorine-containing polyarylethersulfone, and then mixing the synthesized material with TiO2A series of TiO films are prepared by a solution blending mode and a dipping precipitation phase inversion film preparation process2Ultrafiltration membrane of fluorinated polyarylethersulfone, and finally complexing with the prepared PVA solutionCombining to obtain a composite ultrafiltration membrane; the invention also provides the composite ultrafiltration membrane prepared by the preparation method. The composite ultrafiltration membrane has excellent separation performance, self-cleaning anti-pollution anti-aging and self-repairing capabilities, 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 polyarylether sulfone self-repairing reactive composite ultrafiltration membrane and a preparation method thereof.
Background
The membrane separation technology is a novel high-efficiency separation technology for separating, enriching and purifying a mixture through the selective permeability of a membrane under the promotion of external energy or chemical potential difference. It is now one of the best emerging technologies developed today. The membrane separation technology has the advantages of simple separation process, low energy consumption, small medicament dosage, high separation efficiency, convenient operation and the like, so that the membrane separation technology has huge application prospects in the fields of water treatment, food processing, petrochemical industry and the like. Ultrafiltration is a membrane separation technology using pressure difference as driving force, has the functions of concentrating, separating and purifying macromolecular substances, and has better interception effect on colloid, protein and other macromolecular substances. At present, a plurality of organic polymer materials such as polyether sulfone, polyether ketone, polyacrylonitrile, polyvinylidene fluoride and the like are used for preparing an ultrafiltration membrane, and some materials such as polyaniline, polyphenylene oxide and the like are in the research stage. The most representative of the ultrafiltration membrane materials is polyether sulfone (PES) type ultrafiltration membrane material. The material is easy to form a film, excellent in mechanical property, good in thermal stability and long in service life, and therefore, the material can be suitable for ultrafiltration treatment of various kinds of sewage. However, due to the strong hydrophobicity of polyethersulfone, the ultrafiltration membrane is very easy to cause membrane pollution in the using process, which causes the effective pore size of the membrane to be reduced or blocked, resulting in the significant decrease of the permeation flux and the separation performance of the membrane, which also becomes a main bottleneck 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 at present, the self-repairing performance of the prepared composite material can be further endowed on the basis of keeping the excellent self-cleaning performance of the matrix material, and the method is an effective way for solving the pollution problem of the macromolecular ultrafiltration membrane. According to the thought, on one hand, the filler with photocatalytic degradation capability is introduced into an ultrafiltration membrane system, so that the ultrafiltration membrane is endowed with active self-cleaning capability in the separation process; on the other hand, the ultrafiltration membrane is soaked in the hydrogel through physical coating, so that the anti-aging and self-repairing capabilities are endowed to the ultrafiltration membrane.
Among the various types of inorganic photocatalysts, TiO2The photocatalyst is insoluble in water, non-toxic, pollution-free, low in price and high in photocatalytic oxidation activity, and is concerned. At present, it has been found that thousands of difficult to degrade organic pollutants can pass through TiO under the irradiation of ultraviolet rays2And is degraded rapidly. However, in the case of continuous illumination of the ultrafiltration membrane, the degradation thereof is caused to drastically reduce the service life. Therefore, the above problems are to be solved by introducing PVA hydrogel having a good self-repairing effect. The swelling capacity of PVA hydrogel is a cause of self-repair, and when the PVA hydrogel is exposed to water, the hydrogel in the composite material expands to fill the damaged area. Meanwhile, the reversible physical crosslinking function exists between the hydrogel and the high polymer material, so that the hydrogel and the high polymer material can be tightly combined, and the self-repairing performance of the composite material is endowed. In conclusion, the preparation of the ultrafiltration membrane with self-repairing reactivity by compounding the hydrogel and the anti-pollution hybrid ultrafiltration membrane has profound significance in the aspects of solving membrane pollution, membrane aging and membrane repairing.
Disclosure of Invention
The invention aims to provide a PVA/titanium dioxide-fluorine-containing polyarylether sulfone 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 polyarylether sulfone self-repairing reactive composite ultrafiltration membrane, which comprises the following specific steps:
the method comprises the following steps: adding hexafluorobisphenol A, fluorosulfone, a salt forming agent, a reaction solvent and a water-carrying agent into a reaction vessel for reaction to obtain a fluorine-containing polyarylether sulfone polymer matrix material, wherein the structure of the fluorine-containing polyarylether sulfone polymer matrix material is shown as a formula I:
in the formula I, n is the polymerization degree, and n is 50-500;
step two: preparing the fluorine-containing polyarylethersulfone polymer base material prepared in the step one and TiO2Dissolving and dispersing the additive and the additive in an organic solvent, stirring to prepare a homogeneous membrane casting solution, filtering, standing, degassing, casting the membrane casting solution into a membrane after the degassing is completed, keeping the membrane casting solution evaporated for 20-40 seconds in air, then soaking the membrane casting solution into deionized water to form a membrane, and performing post-treatment to obtain the x% TiO2Ultrafiltration membrane of poly (aryl ether sulfone) containing fluorine, in which "x" represents TiO in the membrane2Mass fraction of (a);
step three: mixing the polyvinyl alcohol solution with the sodium borate decahydrate solution to obtain a mixed solution, and then mixing the x% TiO obtained in the second step2And (3) placing the fluorine-containing polyarylether sulfone ultrafiltration membrane into the mixed solution for soaking, and cleaning the surface to obtain the PVA/titanium dioxide-fluorine-containing polyarylether sulfone 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 2-3 hours at 125-145 ℃ and then for 6-8 hours at 170-180 ℃.
Preferably, the value range of x in the second step is 1-5%.
Preferably, the step two additive is polyvinylpyrrolidone.
Preferably, the step two organic solvent is N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), or Tetrahydrofuran (THF).
Preferably, the mass fraction of the fluorine-containing polyarylethersulfone in the casting solution of the second step is 17%.
Preferably, the mass fraction of the solute in the solution of trimeric vinyl alcohol is 15%, and the concentration of the solute in the solution of sodium borate decahydrate is 0.1 mol per liter.
Preferably, the soaking time in the third step is 6-8 hours.
The invention also provides the PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane prepared by the preparation method.
The invention has the advantages of
The invention provides a PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane and a preparation method thereof, the method synthesizes an anti-aging fluorine-containing polyarylether sulfone, then the synthesized material and a certain proportion of inorganic filler titanium dioxide are mixed in a solution mode, a series of titanium dioxide-fluorine-containing polyarylether sulfone ultrafiltration membranes are prepared by using a dipping precipitation phase inversion membrane preparation process, the hydrophilicity of the ultrafiltration membrane is improved by introduced inorganic titanium dioxide particles with photocatalytic activity, and pollutants attached to the ultrafiltration membrane can be degraded, so that the pure water flux of the hybrid ultrafiltration membrane is obviously improved, the polyacrylamide solution flux is also slightly improved, and the separation performance of the prepared titanium dioxide-fluorine-containing polyethersulfone hybrid ultrafiltration membrane is improved. Finally, in order to prevent the pollutants attached to the ultrafiltration membrane from being degraded, a small-amplitude aging effect on the fluorine-containing polyether sulfone matrix material can be generated, so that the service life of the titanium dioxide-fluorine-containing polyarylether sulfone hybrid ultrafiltration membrane is shortened. The 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 in the damaged part of the membrane after the membrane is damaged due to the water absorption performance and the swelling performance of the PVA hydrogel, so that the water flux and the retention rate of the membrane are restored to the original level, and the composite ultrafiltration membrane is endowed with the self-repairing performance.
The PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane provided by the invention has excellent separation performance, self-cleaning anti-pollution anti-aging and self-repairing capabilities, 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 curve of flux over time for a series of PVA/titania-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in example 1, example 2 and example 3 in four operating steps.
FIG. 2 shows the total contamination parameters (R) of the series of PVA/titania-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in examples 1, 2 and 3 in PAM ultrafiltration experimentst) Reversible contamination parameter (R)r) And irreversible fouling parameter (R)ir) Summary of (1) summary of the drawings.
Fig. 3 is a graph of the water flux recovery efficiency of the series of PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in examples 1, 2 and 3 before and after 30 minutes of simulated sunlight irradiation.
Fig. 4 is a graph of the retention rate values of the series of PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in examples 1, 2 and 3 before and after 30 minutes of simulated solar illumination.
Detailed Description
The invention provides a PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane and a preparation method thereof, and the preparation method specifically comprises the following steps:
the method comprises the following steps: mixing hexafluorobisphenol A, fluorosulfone, a salt forming 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 the water-carrying agent and water in the reaction process, reacting at 170-180 ℃ for 6-8 hours, and washing and drying reactants to obtain the fluorine-containing polyarylether sulfone polymer base material.
According to the invention, the salt former is preferably anhydrous potassium carbonate (K)2CO3) The reaction solvent is preferably sulfolane (TMS), and the water-carrying agent is preferably toluene.
According to the present invention, the molar ratio of said hexafluorobisphenol a to fluorosulfone is preferably 1: 1; the molar ratio of the fluorosulfone to the salt forming agent is preferably (0.01-0.05): (0.01 to 0.06); the addition amount of the water-carrying agent is preferably 20-60 ml.
According to the invention, the reaction product is washed and dried, preferably specifically: slowly pouring viscous liquid generated in a reaction container into deionized water to obtain a flexible thin strip product, washing the product for 3-5 times by the deionized water, crushing the product into fine granular substances by a high-speed tissue triturator, boiling and washing the fine granular substances for 3-5 times by deionized water and absolute ethyl alcohol respectively to remove residual solvent, unreacted monomer and micromolecular substances in a 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 base material. The structure is shown as formula I:
in the formula I, n is the polymerization degree, and n is 50-500;
step two: the fluorine-containing polyarylethersulfone polymer base material obtained in the step one and TiO2Dissolving the additive and an additive in an organic solvent, preferably stirring for 12-24 hours at the room temperature of 25 ℃ to prepare a homogeneous casting solution, preferably selecting the additive as polyvinylpyrrolidone (PVP), preferably selecting the organic solvent as N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) or Tetrahydrofuran (THF), filtering the obtained casting solution by using a filter cloth to remove impurities, preferably standing for 12-24 hours, placing the solution 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 casting solution into a film by using a clean film pushing instrument, keeping the casting solution in the air at the room temperature of 25 ℃ for evaporating for 20-40 seconds, then soaking the casting solution into deionized water at 15-25 ℃ to form the film, and performing post-treatment to obtain x% TiO2Ultrafiltration membrane of poly (aryl ether sulfone) containing fluorine, in which "x" represents TiO in the membrane2Mass fraction of (a); the post-treatment preferably comprises: the water bath was replaced 6 times within 48 hours, the solvent and water-soluble polymer additive were completely removed from the membrane, after which the membrane was kept in distilled water to be tested.
According to the invention, the fluorine-containing polyarylethersulfone polymer base material and TiO2And the additive are preferably present in a mass ratio of 100: 1-5: 10; TiO 22-fluorinated polyethersulfone hybrid ultrafiltrationThe mass fraction of the fluorine-containing polyarylethersulfone polymer in the membrane casting solution is preferably 17%.
According to the invention, the thickness of the film on the scale of the film pushing instrument is preferably 0.5 mm.
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 a sodium borate decahydrate solution; and (2) mixing the polyvinyl alcohol solution with a sodium borate decahydrate solution to obtain a mixed solution, placing the titanium dioxide-fluorine-containing polyarylether sulfone ultrafiltration membrane obtained in the step two into the prepared mixed solution for fully 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 polyarylether sulfone self-repairing reactive composite ultrafiltration membrane.
According to the invention, the mass fraction of solute in the polyvinyl alcohol solution in the step three is 15%; the concentration of solute in the sodium borate decahydrate solution is 0.1 moles per liter and the volume ratio of polyvinyl alcohol solution to sodium borate decahydrate solution is preferably 17: 50.
The composite ultrafiltration membrane has better performance with more titanium dioxide, preferably between 1 and 5 percent and more preferably 5 percent, but is easy to run out of the membrane with more titanium dioxide, is not suitable for application, so the content of the titanium dioxide should be reasonably controlled.
The invention also provides the PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane prepared by the preparation method.
The present invention is described in further detail below with reference to specific examples, in which the starting materials are all 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), a sulfolane solvent (46 ml) and a toluene water-carrying agent (25 ml) were sequentially added to a 100 ml three-necked 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 heating to 130 ℃ for reflux reaction for 3 hours, then removing the toluene as the water-carrying agent and the water in the reaction process, continuing heating to 175 ℃ for reaction for 7 hours, after the polymer becomes viscous, pouring the polymer into deionized water, boiling and washing with the deionized water and absolute ethyl alcohol respectively for 5 times, removing residual solvent, unreacted monomer and small molecular substances in the crude product, and finally carrying out vacuum drying on the product in a vacuum oven at 60 ℃ for 36 hours to obtain the fluorine-containing polyarylethersulfone material.
2) Dissolving 0.0194 g of titanium dioxide, 1.938 g of fluorine-containing polyarylethersulfone and 0.193 g of additive polyvinylpyrrolidone (PVP) in 20 ml of organic solvent N, N-Dimethylformamide (DMF), stirring for 18 hours to prepare a homogeneous membrane casting solution, filtering the solution by using filter cloth to remove impurities, standing for 12 hours, placing the solution in a vacuum oven for degassing at 50 ℃, casting the membrane casting solution on a glass plate paved with polyester non-woven fabric after complete degassing, scraping the membrane by using a clean scraper, keeping the membrane casting solution in air for evaporating for 30 seconds at the room temperature of 25 ℃, and then immersing the membrane casting solution in deionized water to form the membrane. Thereafter, the water bath was replaced 6 times within 48 hours, the solvent and the water-soluble polymer additive were completely removed from the membrane, and thereafter the membrane was kept in distilled water for use. The prepared hybrid membrane was named 1% TiO2Fluorine-containing polyarylethersulfones, where "x" denotes TiO in the hybrid membrane2Mass fraction of (c).
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, 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 is added into a 200 ml beaker, 100 ml of deionized water is added, and after complete dissolution, the mixture is poured into a polyvinyl alcohol solution to form a mixed solution. Soaking the 1% titanium dioxide-fluorine-containing polyarylether sulfone ultrafiltration membrane prepared in the step 2) in the mixed solution for 7 hours, then taking out the ultrafiltration membrane, and cleaning the surface of the membrane by using deionized water to obtain the PVA/1% titanium dioxide-fluorine-containing polyarylether sulfone 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 fluorine-containing polyether sulfone and 0.193 g of additive polyvinylpyrrolidone (PVP) are dissolved in 20 ml of organic solvent N, N-Dimethylformamide (DMF), and the mixture is stirred for 18 hours to prepare a homogeneous membrane casting solution. The solution was then filtered through a filter cloth to remove impurities, left for 12 hours and degassed in a vacuum oven at 50 ℃. And after complete degassing, casting the casting solution on a glass plate paved with polyester non-woven fabric, scraping the casting solution into a film by using a clean scraper, evaporating the casting solution in the air for 30 seconds at the room temperature of 25 ℃, and then soaking the casting solution into deionized water to form the film. Thereafter, the water bath was replaced 6 times within 48 hours, the solvent and the water-soluble polymer additive were completely removed from the membrane, and thereafter the membrane was kept in distilled water for use. The prepared hybrid membrane was named 3% titania-fluoropolysulfone, 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, 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 is added into a 200 ml beaker, 100 ml of deionized water is added, and after complete dissolution, the mixture is poured into a polyvinyl alcohol solution to form a mixed solution. Soaking the 3% titanium dioxide-fluorine-containing polyarylether sulfone ultrafiltration membrane prepared in the step 2) in the mixed solution for 7 hours, then taking out the ultrafiltration membrane, and cleaning the surface of the membrane by using deionized water to finally obtain the PVA/3% titanium dioxide-fluorine-containing polyarylether sulfone 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 fluorine-containing polyether sulfone and 0.193 g of additive polyvinylpyrrolidone (PVP) are dissolved in 20 ml of organic solvent N, N-Dimethylformamide (DMF), and the mixture is stirred for 12 hours to prepare a homogeneous membrane casting solution. The solution was then filtered through a filter cloth to remove impurities, left for 12 hours and degassed in a vacuum oven at 50 ℃. And after complete degassing, casting the casting solution on a glass plate paved with polyester non-woven fabric, scraping the casting solution into a film by using a clean scraper, keeping the casting solution evaporated for 30 seconds in the air at the room temperature of 25 ℃, and then soaking the casting solution into deionized water to form the film. Thereafter, the water bath was replaced 6 times within 48 hours, the solvent and the water-soluble polymer additive were completely removed from the membrane, and thereafter the membrane was kept in distilled water for use. The prepared hybrid membrane was named 5% titania-fluoropolysulfone, 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, 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 is added into a 200 ml beaker, 100 ml of deionized water is added, and after complete dissolution, the mixture is poured into a polyvinyl alcohol solution to form a mixed solution. Soaking the 5% titanium dioxide-fluorine-containing polyarylether sulfone ultrafiltration membrane prepared in the step 2) in the mixed solution for 7 hours, then taking out the ultrafiltration membrane, and cleaning the surface of the membrane by using deionized water to finally obtain the PVA/5% titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane.
FIG. 1 is a graph of flux over time for a series of PVA/titania-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in example 1, example 2 and example 3 above in four operating steps. The four operation steps are respectively as follows: testing the pure water flux of the membrane for 15 minutes, testing the pure water flux of the membrane for 30 minutes after hydraulic cleaning, and testing the pure water flux of the membrane for 30 minutes after simulating the solar illumination for 30 minutes.
FIG. 1 illustrates: in the content interval of the titanium dioxide, the PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane has the advantage that the pure water flux is increased along with the increase of the content of the titanium dioxide, and the hydrophilicity of the ultrafiltration membrane is further improved due to the increase of the content of the titanium dioxide. In addition, the ultrafiltration membranes have low flux to the polyacrylamide solution, which is caused by the pollution of the ultrafiltration membranes by polyacrylamide. After the ultrafiltration membrane is cleaned by water power, the pure water flux of the PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane still increases along with the increase of the content of the titanium dioxide, the introduction of the titanium dioxide increases the hydrophilicity of the ultrafiltration membrane, so that pollutants are easier to remove in the process of water power cleaning, and the pollution resistance of the ultrafiltration membrane is obviously improved. In addition, from the data in fig. 1, it can be found that after the PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane is irradiated by simulated solar light, the pure water flux is remarkably increased, because the inorganic titanium dioxide nanoparticles can degrade part of pollutants attached to the ultrafiltration membrane through photocatalytic oxidation, so that the hybrid ultrafiltration membrane is endowed with a certain self-cleaning capability, and the anti-pollution capability of the hybrid ultrafiltration membrane is further enhanced.
FIG. 2 shows the total contamination parameters (R) of the series of PVA/titania-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membranes prepared in the above-mentioned examples 1, 2 and 3 in the PAM ultrafiltration experimentt) Reversible contamination parameter (R)r) And irreversible fouling parameter (R)ir) Summary of (1) summary of the drawings. Analysis of the data in fig. 2 shows that, in the process of testing the anti-contamination performance of the ultrafiltration membrane, the total contamination coefficients of the ultrafiltration membrane are all large and reach more than 90%, which is mainly caused by the large pure water flux of the ultrafiltration membrane. However, with the increase of the content of the titanium dioxide, the reversible pollution parameter of the ultrafiltration membrane is gradually increased, and the irreversible pollution parameter is gradually reduced, because the introduction of the titanium dioxide with different content 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 of PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membranes prepared in the above embodiments 1, 2 and 3 before and after the simulated sunlight irradiation for 30 min. From the data in fig. 3, it can be found that the flux recovery efficiency increases significantly with the increase in the content of titanium dioxide in the ultrafiltration membrane. The inorganic titanium dioxide particles in the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane can degrade partial pollutants attached to the ultrafiltration membrane through photocatalytic oxidation after being irradiated by simulated solar light, so that the hybrid ultrafiltration membrane has certain self-cleaning capability.
Fig. 4 is a numerical value of the retention rate of the series of 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 solar illumination. As can be seen from the figure, the retention rate of the composite ultrafiltration membrane with different titanium dioxide contents is almost unchanged, which shows that PVA endows the ultrafiltration membrane with self-repairing performance.
Claims (10)
1. A preparation method of a PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane is characterized by comprising the following specific steps:
the method comprises the following steps: adding hexafluorobisphenol A, fluorosulfone, a salt forming agent, a reaction solvent and a water-carrying agent into a reaction vessel for reaction to obtain a fluorine-containing polyarylether sulfone polymer matrix material, wherein the structure of the fluorine-containing polyarylether sulfone polymer matrix material is shown as a formula I:
in the formula I, n is the polymerization degree, and n is 50-500;
step two: preparing the fluorine-containing polyarylethersulfone polymer base material prepared in the step one and TiO2Dissolving and dispersing the additive and the additive in an organic solvent, stirring to prepare a homogeneous membrane casting solution, filtering, standing, degassing, casting the membrane casting solution into a membrane after the degassing is completed, keeping the membrane casting solution evaporated for 20-40 seconds in air, then soaking the membrane casting solution into deionized water to form a membrane, and performing post-treatment to obtain the x% TiO2Ultrafiltration membrane of fluorinated polyarylethersulfone, where x represents TiO in the membrane2Mass fraction of (a);
step three: mixing the polyvinyl alcohol solution with the sodium borate decahydrate solution to obtain a mixed solution, and then mixing the x% TiO obtained in the second step2And (3) placing the fluorine-containing polyarylether sulfone ultrafiltration membrane into the mixed solution for soaking, and cleaning the surface to obtain the PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane.
2. The preparation method of the PVA/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein a salt forming agent in the step is anhydrous potassium carbonate, a water carrying agent is toluene, and a reaction solvent is sulfolane.
3. The preparation method of 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 at 125-145 ℃ for 2-3 hours, and then at 170-180 ℃ for 6-8 hours.
4. The preparation method of 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 preparation method of 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 preparation method of the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein the organic solvent in the second step is N, N-dimethylformamide, N-dimethylacetamide or tetrahydrofuran.
7. The preparation method of the PVA/titanium dioxide-fluorine-containing polyarylethersulfone self-repairing reactive composite ultrafiltration membrane according to claim 1, wherein the mass fraction of the fluorine-containing polyarylethersulfone in the membrane casting solution in the second step is 17%.
8. The preparation method of the 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 solution of the trimeric vinyl alcohol is 15%, and the concentration of the solute in the solution of sodium borate decahydrate is 0.1 mol/L.
9. The preparation method of 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/titanium dioxide-fluorine-containing polyarylether sulfone self-repairing reactive composite ultrafiltration membrane prepared by the preparation method of claim 1.
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