CN117983073A - Antibacterial and anti-pollution microporous membrane and preparation method thereof - Google Patents
Antibacterial and anti-pollution microporous membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antibacterial and anti-pollution microporous membrane and a preparation method thereof, which relate to the technical field of membrane material preparation for water treatment and are prepared from the following raw materials in parts by weight: 50-60 parts of polyethersulfone, 35-45 parts of polyvinylidene fluoride, 8-10 parts of porous zinc oxide nano powder, 15-25 parts of pore-forming agent, 1-3 parts of coupling agent, 2-4 parts of compatilizer, 5-8 parts of reactive beta-cyclodextrin quaternary ammonium salt, 3-5 parts of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 0.1-0.3 part of brominated 3-allylbenzothiazole and 1-3 parts of N-acryloylmorpholine. The membrane has good antibacterial and anti-pollution properties and sufficient water flux.
Description
Technical Field
The invention relates to the technical field of preparation of membrane materials for water treatment, in particular to an antibacterial and anti-pollution microporous membrane and a preparation method thereof.
Background
The membrane separation technology has the functions of separation, purification, concentration, refining and the like, has the advantages of high separation efficiency, small occupied area, low energy consumption, simple and convenient operation, energy conservation, environmental protection and the like, becomes one of the most important means in the current separation science, and is widely applied to the fields of water treatment, chemical industry, environmental protection, food, medicine and the like. Microporous membranes are one of the indispensable materials in membrane separation technology, and their performance directly affects the membrane separation effect. It is seen that the development of microporous membranes with excellent overall performance and performance stability is particularly important.
When the microporous membrane is used, the microporous membrane is easily polluted by pollutants in water, including natural organic matters, saccharides, proteins and the like, so that the pollutants are irreversibly adsorbed on the surface of the microporous membrane and pore channels of the microporous membrane, and the service performance of the microporous membrane is reduced; in addition, in the treatment process, microorganisms such as bacteria in the water body can adhere to the surfaces of the microporous membranes and the pore channels of the microporous membranes, and organic matters in the water or adhered to the membranes provide nutrition for the microorganisms, so that the growth of the microorganisms on the surfaces of the microporous membranes and the pore channels of the microporous membranes is promoted, and biological pollution is caused. It is in this situation that antimicrobial and anti-fouling microporous membranes have been developed, and their advent has attracted considerable attention in the industry.
The traditional antibacterial and anti-pollution microporous membrane has the technical defects of further improvement of antibacterial and anti-pollution performance, insufficient membrane water flux, limited interception and separation effects and the like. The main microporous membranes on the market at present comprise polyvinylidene fluoride (PVDF) microporous membranes and polyether sulfone (PES) microporous membranes, and the polyvinylidene fluoride microporous membranes have the advantages of small filter pore diameter, high mechanical strength, wide application range and the like, but have the defects of easy blockage and high price, while the polyether sulfone has the advantages of strong stability, corrosion resistance, creep resistance and the like, but have the defect of easy wire breakage. Under the situation, the PVDF/PES blended composite microporous membrane is generated, however, the existing PVDF/PES blended composite microporous membrane still has the defects of insufficient water flux, no bacteria resistance, pollution resistance and the like.
For example, the Chinese patent publication No. CN115382400B discloses a high-flux PVDF/PES blend membrane and a preparation method thereof, wherein the high-flux PVDF/PES blend membrane is prepared from the following raw materials in parts by weight: 50-65 parts of high polymer resin powder, 85-105 parts of solvent, 2-7 parts of additive, 10-25 parts of pore-forming agent, modifier, curing agent and core liquid. The PVDF/PES blend membrane has good hydrophilicity, permeability and continuous anti-pollution performance, however, the PVDF/PES blend membrane still has no antibacterial function, and is easy to cause biological pollution and reduce the use performance.
Therefore, the development of the antibacterial and anti-pollution microporous membrane with good antibacterial and anti-pollution properties and sufficient water flux and the preparation method thereof meet the market demand, have wide market value and application prospect, and have very important significance for promoting the development of the microporous membrane field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an antibacterial and anti-pollution microporous membrane with good antibacterial and anti-pollution performance and sufficient water flux and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme: an antibacterial and anti-pollution microporous membrane is prepared from the following raw materials in parts by weight: 50-60 parts of polyethersulfone, 35-45 parts of polyvinylidene fluoride, 8-10 parts of porous zinc oxide nano powder, 15-25 parts of pore-forming agent, 1-3 parts of coupling agent, 2-4 parts of compatilizer, 5-8 parts of reactive beta-cyclodextrin quaternary ammonium salt, 3-5 parts of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 0.1-0.3 part of brominated 3-allylbenzothiazole and 1-3 parts of N-acryloylmorpholine.
Preferably, the polyethersulfone is provided in Sorvy (Suwei) under the trademark3000MP polyethersulfone.
Preferably, the polyvinylidene fluoride is provided by Acomax under the brand KYNAR2501-20 Of polyvinylidene fluoride.
Preferably, the source of the porous zinc oxide nano powder is not particularly required, and in one embodiment of the present invention, the porous zinc oxide nano powder is prepared according to the method of embodiment 2 in chinese patent No. CN 101318690B.
Preferably, the pore-forming agent is any one of polyvinylpyrrolidone K-30, polyethylene glycol 1000, polyvinylpyrrolidone K-17, polyvinylpyrrolidone K-60, polyvinylpyrrolidone K-90, polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600.
Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
Preferably, the compatilizer is at least one of compatilizer ABS-g-MAH and compatilizer PE-g-MAH.
Preferably, the source of the reactive beta-cyclodextrin quaternary ammonium salt is not particularly limited, and in one embodiment of the present invention, the beta-cyclodextrin quaternary ammonium salt is prepared according to the method of example 5 in chinese patent No. CN 106008755B.
Another object of the present invention is to provide a method for preparing the antibacterial and anti-pollution microporous membrane, comprising the steps of:
Step S1, adding polyethersulfone, polyvinylidene fluoride, porous zinc oxide nano powder, a pore-forming agent, a compatilizer and a coupling agent into an organic solvent, performing ultrasonic treatment for 10-20min, and uniformly stirring to obtain a casting solution; removing the solvent, cleaning with deionized water, and naturally airing to obtain a primary membrane;
S2, uniformly mixing reactive beta-cyclodextrin quaternary ammonium salt, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, brominated 3-allylbenzothiazole and N-acryloylmorpholine to obtain a mixture, and uniformly dispersing the mixture in methanol to obtain a modified dispersion; and then soaking the primary membrane in the modified dispersion liquid, irradiating by adopting 60 Co-gamma ray source under nitrogen atmosphere, and then washing and drying sequentially to obtain the antibacterial and anti-pollution microporous membrane.
Preferably, the ultrasonic power of the ultrasonic treatment in the step S1 is 200W; the organic solvent is any one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide.
Preferably, in the step S2, the mass ratio of the mixture to the methanol is 1 (5-8).
Preferably, the irradiation in the step S2 is performed at room temperature, the irradiation dose rate is 10-420 Gy/min, and the irradiation dose is 10-55 kGy.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) The preparation method of the antibacterial and anti-pollution microporous membrane disclosed by the invention has the advantages of simple process, convenient operation control, high preparation efficiency and finished product qualification rate, low equipment dependence and low energy consumption, is suitable for continuous large-scale production, and has higher popularization and application values.
(2) The invention discloses an antibacterial anti-pollution microporous membrane which is prepared from the following raw materials in parts by weight: 50-60 parts of polyethersulfone, 35-45 parts of polyvinylidene fluoride, 8-10 parts of porous zinc oxide nano powder, 15-25 parts of pore-forming agent, 1-3 parts of coupling agent, 2-4 parts of compatilizer, 5-8 parts of reactive beta-cyclodextrin quaternary ammonium salt, 3-5 parts of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 0.1-0.3 part of brominated 3-allylbenzothiazole and 1-3 parts of N-acryloylmorpholine. Through the mutual cooperation and coaction of the raw materials, the prepared microporous membrane has good antibacterial and anti-pollution properties and sufficient water flux. Meanwhile, polyether sulfone and polyvinylidene fluoride are used as base materials, the advantages of the polyether sulfone and the polyvinylidene fluoride are combined, and the compatibility of the raw materials can be improved through the addition of the compatilizer, the coupling agent and other auxiliary agents; the interpenetrating network structure is formed by surface radiation grafting modification, so that the stability of the material structure and performance can be further improved, and the service life of the material can be further effectively prolonged.
(3) The invention discloses an antibacterial and anti-pollution microporous membrane, which is modified by surface radiation grafting, and the monomers containing unsaturated ethylenic bonds, such as reactive beta-cyclodextrin quaternary ammonium salt, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, brominated 3-allylbenzothiazole and N-acryloylmorpholine, can be grafted with cyclodextrin quaternary ammonium salt, amphoteric organic ion salt, benzothiazole salt and morpholine structures on the surface of the microporous membrane, and the structures can endow the microporous membrane with excellent antibacterial and anti-pollution performance under the multiple effects of electronic effect, steric effect and conjugation effect, so that the prepared membrane has sufficient water flux. The reactive beta-cyclodextrin quaternary ammonium salt is selected from raw materials containing a plurality of unsaturated olefinic bonds, and an interpenetrating network structure is formed on the surface of the membrane in the radiation grafting modification process, so that the structure and the performance stability of the microporous membrane are further improved, and the service life of the microporous membrane is prolonged.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
An antibacterial and anti-pollution microporous membrane is prepared from the following raw materials in parts by weight: 50 parts of polyethersulfone, 35 parts of polyvinylidene fluoride, 8 parts of porous zinc oxide nano powder, 15 parts of pore-forming agent, 1 part of coupling agent, 2 parts of compatilizer, 5 parts of reactive beta-cyclodextrin quaternary ammonium salt, 3 parts of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 0.1 part of brominated 3-allylbenzothiazole and 1 part of N-acryloylmorpholine.
The polyethersulfone is provided with the Sorvo (Suwei) brand3000MP polyethersulfone; the brand of polyvinylidene fluoride provided for the Acomax is KYNAR/>2501-20 Of polyvinylidene fluoride; the porous zinc oxide nano powder is prepared according to the method of the example 2 in the Chinese invention patent CN 101318690B; the pore-forming agent is polyvinylpyrrolidone K-30; the coupling agent is a silane coupling agent KH550; the compatilizer is compatilizer ABS-g-MAH; the beta-cyclodextrin quaternary ammonium salt is prepared according to the method of example 5 in Chinese patent No. CN 106008755B.
The preparation method of the antibacterial and anti-pollution microporous membrane comprises the following steps:
Step S1, adding polyethersulfone, polyvinylidene fluoride, porous zinc oxide nano powder, a pore-forming agent, a compatilizer and a coupling agent into an organic solvent, performing ultrasonic treatment for 10min, and uniformly stirring to obtain a casting solution; removing the solvent, cleaning with deionized water, and naturally airing to obtain a primary membrane; the ultrasonic power of the ultrasonic treatment is 200W; the organic solvent is dimethyl sulfoxide;
S2, uniformly mixing reactive beta-cyclodextrin quaternary ammonium salt, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, brominated 3-allylbenzothiazole and N-acryloylmorpholine to obtain a mixture, and uniformly dispersing the mixture in methanol to obtain a modified dispersion; then soaking the primary membrane in the modified dispersion liquid, irradiating with 60 Co-gamma ray source under nitrogen atmosphere, and then washing and drying sequentially to obtain the antibacterial and anti-pollution microporous membrane; the mass ratio of the mixture to the methanol is 1:5; the irradiation in the step S2 is performed at room temperature, the irradiation dose rate is 10Gy/min, and the irradiation dose is 10kGy. Through weight change and element analysis, it is confirmed that the reactive beta-cyclodextrin quaternary ammonium salt, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, brominated 3-allylbenzothiazole and N-acryloylmorpholine all undergo grafting reaction, and the proportion of the monomers participating in the reaction is 4.98:2.99:0.1:0.97. The final film was subjected to melt and dissolution experiments, and the results were insoluble and infusible, indicating that an interpenetrating network structure was formed.
Example 2
An antibacterial and anti-pollution microporous membrane is prepared from the following raw materials in parts by weight: 53 parts of polyethersulfone, 37 parts of polyvinylidene fluoride, 8.5 parts of porous zinc oxide nano powder, 17 parts of pore-forming agent, 1.5 parts of coupling agent, 2.5 parts of compatilizer, 6 parts of reactive beta-cyclodextrin quaternary ammonium salt, 3.5 parts of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 0.15 part of brominated 3-allylbenzothiazole and 1.5 parts of N-acryloylmorpholine.
The polyethersulfone is provided with the Sorvo (Suwei) brand3000MP polyethersulfone; the brand of polyvinylidene fluoride provided for the Acomax is KYNAR/>2501-20 Of polyvinylidene fluoride; the porous zinc oxide nano powder is prepared according to the method of the example 2 in the Chinese invention patent CN 101318690B; the pore-forming agent is polyethylene glycol 1000; the coupling agent is silane coupling agent KH560; the compatilizer is compatilizer PE-g-MAH; the beta-cyclodextrin quaternary ammonium salt is prepared according to the method of example 5 in Chinese patent No. CN 106008755B.
The preparation method of the antibacterial and anti-pollution microporous membrane comprises the following steps:
Step S1, adding polyethersulfone, polyvinylidene fluoride, porous zinc oxide nano powder, a pore-forming agent, a compatilizer and a coupling agent into an organic solvent, performing ultrasonic treatment for 10-20min, and uniformly stirring to obtain a casting solution; removing the solvent, cleaning with deionized water, and naturally airing to obtain a primary membrane; the organic solvent is N, N-dimethylformamide;
S2, uniformly mixing reactive beta-cyclodextrin quaternary ammonium salt, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, brominated 3-allylbenzothiazole and N-acryloylmorpholine to obtain a mixture, and uniformly dispersing the mixture in methanol to obtain a modified dispersion; and then soaking the primary membrane in the modified dispersion liquid, irradiating by adopting 60 Co-gamma ray source under nitrogen atmosphere, and then washing and drying sequentially to obtain the antibacterial and anti-pollution microporous membrane.
The ultrasonic power of the ultrasonic treatment in the step S1 is 200W; in the step S2, the mass ratio of the mixture to the methanol is 1:6; the irradiation in the step S2 is performed at room temperature, the irradiation dose rate is 100Gy/min, and the irradiation dose is 25kGy.
Example 3
An antibacterial and anti-pollution microporous membrane is prepared from the following raw materials in parts by weight: 55 parts of polyethersulfone, 40 parts of polyvinylidene fluoride, 9 parts of porous zinc oxide nano powder, 20 parts of pore-forming agent, 2 parts of coupling agent, 3 parts of compatilizer, 6.5 parts of reactive beta-cyclodextrin quaternary ammonium salt, 4 parts of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 0.2 part of brominated 3-allylbenzothiazole and 2 parts of N-acryloylmorpholine.
The polyethersulfone is provided with the Sorvo (Suwei) brand3000MP polyethersulfone; the brand of polyvinylidene fluoride provided for the Acomax is KYNAR/>2501-20 Of polyvinylidene fluoride; the porous zinc oxide nano powder is prepared according to the method of the example 2 in the Chinese invention patent CN 101318690B; the pore-forming agent is polyvinylpyrrolidone K-17; the coupling agent is a silane coupling agent KH570; the compatilizer is compatilizer ABS-g-MAH; the beta-cyclodextrin quaternary ammonium salt is prepared according to the method of example 5 in Chinese patent No. CN 106008755B.
The preparation method of the antibacterial and anti-pollution microporous membrane comprises the following steps:
Step S1, adding polyethersulfone, polyvinylidene fluoride, porous zinc oxide nano powder, a pore-forming agent, a compatilizer and a coupling agent into an organic solvent, performing ultrasonic treatment for 15min, and uniformly stirring to obtain a casting solution; removing the solvent, cleaning with deionized water, and naturally airing to obtain a primary membrane; the organic solvent is N-methyl pyrrolidone;
S2, uniformly mixing reactive beta-cyclodextrin quaternary ammonium salt, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, brominated 3-allylbenzothiazole and N-acryloylmorpholine to obtain a mixture, and uniformly dispersing the mixture in methanol to obtain a modified dispersion; and then soaking the primary membrane in the modified dispersion liquid, irradiating by adopting 60 Co-gamma ray source under nitrogen atmosphere, and then washing and drying sequentially to obtain the antibacterial and anti-pollution microporous membrane.
The ultrasonic power of the ultrasonic treatment in the step S1 is 200W; in the step S2, the mass ratio of the mixture to the methanol is 1:6.5; the irradiation in the step S2 is performed at room temperature, the irradiation dose rate is 250Gy/min, and the irradiation dose is 35kGy.
Example 4
An antibacterial and anti-pollution microporous membrane is prepared from the following raw materials in parts by weight: 58 parts of polyethersulfone, 43 parts of polyvinylidene fluoride, 9.5 parts of porous zinc oxide nano powder, 23 parts of pore-forming agent, 2.5 parts of coupling agent, 3.5 parts of compatilizer, 7.5 parts of reactive beta-cyclodextrin quaternary ammonium salt, 4.5 parts of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 0.25 part of brominated 3-allylbenzothiazole and 2.5 parts of N-acryloylmorpholine.
The polyethersulfone is provided with the Sorvo (Suwei) brand3000MP polyethersulfone; the brand of polyvinylidene fluoride provided for the Acomax is KYNAR/>2501-20 Of polyvinylidene fluoride; the porous zinc oxide nano powder is prepared according to the method of the example 2 in the Chinese invention patent CN 101318690B; the pore-forming agent is polyvinylpyrrolidone K-60; the coupling agent is a mixture formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to a mass ratio of 1:2:1; the compatilizer is a mixture formed by mixing compatilizer ABS-g-MAH and compatilizer PE-g-MAH according to a mass ratio of 3:5; the beta-cyclodextrin quaternary ammonium salt is prepared according to the method of example 5 in Chinese patent No. CN 106008755B.
The preparation method of the antibacterial and anti-pollution microporous membrane comprises the following steps:
Step S1, adding polyethersulfone, polyvinylidene fluoride, porous zinc oxide nano powder, a pore-forming agent, a compatilizer and a coupling agent into an organic solvent, performing ultrasonic treatment for 18min, and uniformly stirring to obtain a casting solution; removing the solvent, cleaning with deionized water, and naturally airing to obtain a primary membrane; the organic solvent is dimethyl sulfoxide;
S2, uniformly mixing reactive beta-cyclodextrin quaternary ammonium salt, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, brominated 3-allylbenzothiazole and N-acryloylmorpholine to obtain a mixture, and uniformly dispersing the mixture in methanol to obtain a modified dispersion; and then soaking the primary membrane in the modified dispersion liquid, irradiating by adopting 60 Co-gamma ray source under nitrogen atmosphere, and then washing and drying sequentially to obtain the antibacterial and anti-pollution microporous membrane.
The ultrasonic power of the ultrasonic treatment in the step S1 is 200W; in the step S2, the mass ratio of the mixture to the methanol is 1:7.5; the irradiation in the step S2 is performed at room temperature, the irradiation dose rate is 380Gy/min, and the irradiation dose is 45kGy.
Example 5
An antibacterial and anti-pollution microporous membrane is prepared from the following raw materials in parts by weight: 60 parts of polyethersulfone, 45 parts of polyvinylidene fluoride, 10 parts of porous zinc oxide nano powder, 25 parts of pore-forming agent, 3 parts of coupling agent, 4 parts of compatilizer, 8 parts of reactive beta-cyclodextrin quaternary ammonium salt, 5 parts of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 0.3 part of brominated 3-allylbenzothiazole and 3 parts of N-acryloylmorpholine.
The polyethersulfone is provided with the Sorvo (Suwei) brand3000MP polyethersulfone; the brand of polyvinylidene fluoride provided for the Acomax is KYNAR/>2501-20 Of polyvinylidene fluoride; the porous zinc oxide nano powder is prepared according to the method of the example 2 in the Chinese invention patent CN 101318690B; the pore-forming agent is polyethylene glycol 200; the coupling agent is a silane coupling agent KH550; the compatilizer is compatilizer ABS-g-MAH; the beta-cyclodextrin quaternary ammonium salt is prepared according to the method of example 5 in Chinese patent No. CN 106008755B.
The preparation method of the antibacterial and anti-pollution microporous membrane comprises the following steps:
Step S1, adding polyethersulfone, polyvinylidene fluoride, porous zinc oxide nano powder, a pore-forming agent, a compatilizer and a coupling agent into an organic solvent, performing ultrasonic treatment for 20min, and uniformly stirring to obtain a casting solution; removing the solvent, cleaning with deionized water, and naturally airing to obtain a primary membrane; the organic solvent is N, N-dimethylacetamide;
S2, uniformly mixing reactive beta-cyclodextrin quaternary ammonium salt, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, brominated 3-allylbenzothiazole and N-acryloylmorpholine to obtain a mixture, and uniformly dispersing the mixture in methanol to obtain a modified dispersion; and then soaking the primary membrane in the modified dispersion liquid, irradiating by adopting 60 Co-gamma ray source under nitrogen atmosphere, and then washing and drying sequentially to obtain the antibacterial and anti-pollution microporous membrane.
The ultrasonic power of the ultrasonic treatment in the step S1 is 200W; in the step S2, the mass ratio of the mixture to the methanol is 1:8; the irradiation in the step S2 is performed at room temperature, the irradiation dose rate is 420Gy/min, and the irradiation dose is 55kGy.
Comparative example 1
An antibacterial and anti-pollution microporous membrane and a preparation method thereof are basically the same as in example 1, except that no porous zinc oxide nano powder and no N-acryloylmorpholine are added.
Comparative example 2
An antibacterial and anti-fouling microporous membrane and its preparation method are substantially the same as in example 1, except that 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt and 3-allylbenzothiazole bromide are not added.
To further illustrate the beneficial technical effects of the antimicrobial and anti-fouling microporous films according to the embodiments of the present invention, the antimicrobial and anti-fouling microporous films according to examples 1 to 5 and comparative examples 1 to 2 were subjected to the relevant performance test, the test results are shown in table 1, and the test methods are as follows:
(1) Pure water flux: through the cross-flow cell test, the test pressure was 0.1MPa and the flow rate was set at 800mL/min.
(2) Resistance to contamination: placing each microporous membrane sample in a cross-flow cell device, taking 0.5g/L bovine serum albumin solution as a feed liquid, and filtering for 30min; cleaning the device with deionized water, inverting the microporous membrane sample in cross flow, and backflushing for 5min under the pressure of 0.02 MPa; the microporous membrane sample was then reversed, and the pure water flux was measured at 0.1MPa, and the flux recovery rate (flux recovery rate=pure water flux after backwashing/pure water flux×100%) was calculated.
(3) Antibacterial properties: culturing staphylococcus aureus or escherichia coli to a concentration of 108CFU/ml with TSB bacteria based on 37 ℃, and diluting to 107CFU/ml with PBS solution; cutting a microporous membrane sample into a circular sheet with the diameter of 8mm by using a puncher, sterilizing by using 75% alcohol, putting the circular sheet into a porous plate, dripping 10uL of bacteria on the surface of the membrane in an ultra-clean bench, and culturing the porous plate in a constant-temperature shaking box at 37 ℃ for 24 hours; bacterial liquid attached to the microporous membrane sample was washed off with PBS and collected, diluted with PBS solution and plated for counting, and the sterilization rate was calculated (sterilization rate=1-the number of bacterial plaques on the experimental sample/the number of bacterial plaques on the control sample×100%).
TABLE 1
| Project | Pure water flux | Resistance to contamination | Staphylococcus aureus sterilizing rate | E.coli sterilization rate |
| Unit (B) | L·m-2h-1bar-1 | ％ | ％ | ％ |
| Example 1 | 223 | 99.23 | 99.79 | 99.86 |
| Example 2 | 227 | 99.41 | 99.84 | 99.90 |
| Example 3 | 229 | 99.56 | 99.91 | 99.95 |
| Example 4 | 234 | 99.68 | 99.94 | 99.97 |
| Example 5 | 237 | 99.88 | 99.98 | 99.99 |
| Comparative example 1 | 215 | 97.57 | 97.62 | 97.70 |
| Comparative example 2 | 211 | 96.89 | 98.18 | 98.15 |
As can be seen from the data in table 1, the antibacterial and anti-pollution microporous membrane according to each example of the present invention has higher pure water flux, better pollution resistance and antibacterial property than the comparative example; the addition of porous zinc oxide nanopowder, N-acryloylmorpholine, 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt and brominated 3-allylbenzothiazole is beneficial for improving the above properties.
The above embodiments are provided for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications according to the spirit of the present invention should be included in the scope of the present invention.
Claims (9)
1. An antibacterial and anti-pollution microporous membrane is characterized by being prepared from the following raw materials in parts by weight: 50-60 parts of polyethersulfone, 35-45 parts of polyvinylidene fluoride, 8-10 parts of porous zinc oxide nano powder, 15-25 parts of pore-forming agent, 1-3 parts of coupling agent, 2-4 parts of compatilizer, 5-8 parts of reactive beta-cyclodextrin quaternary ammonium salt, 3-5 parts of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 0.1-0.3 part of brominated 3-allylbenzothiazole and 1-3 parts of N-acryloylmorpholine.
2. The antimicrobial anti-fouling microporous membrane according to claim 1, wherein the polyethersulfone is brand namePolyether sulfone of (a).
3. The antimicrobial anti-fouling microporous membrane of claim 1, wherein the polyvinylidene fluoride is of the brandPolyvinylidene fluoride of (a).
4. The antimicrobial and anti-fouling microporous membrane according to claim 1, wherein the porogen is any one of polyvinylpyrrolidone K-30, polyethylene glycol 1000, polyvinylpyrrolidone K-17, polyvinylpyrrolidone K-60, polyvinylpyrrolidone K-90, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600.
5. The antimicrobial and anti-fouling microporous membrane according to claim 1, wherein the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560, and a silane coupling agent KH 570.
6. The antimicrobial anti-fouling microporous membrane according to claim 1, wherein the compatibilizer is at least one of ABS-g-MAH and PE-g-MAH.
7. A method of making an antimicrobial, anti-fouling microporous membrane according to any one of claims 1 to 6, comprising the steps of:
Step S1, adding polyethersulfone, polyvinylidene fluoride, porous zinc oxide nano powder, a pore-forming agent, a compatilizer and a coupling agent into an organic solvent, performing ultrasonic treatment for 10-20min, and uniformly stirring to obtain a casting solution; removing the solvent, cleaning with deionized water, and naturally airing to obtain a primary membrane;
S2, uniformly mixing reactive beta-cyclodextrin quaternary ammonium salt, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, brominated 3-allylbenzothiazole and N-acryloylmorpholine to obtain a mixture, and uniformly dispersing the mixture in methanol to obtain a modified dispersion; and then soaking the primary membrane in the modified dispersion liquid, irradiating by adopting 60 Co-gamma ray source under nitrogen atmosphere, and then washing and drying sequentially to obtain the antibacterial and anti-pollution microporous membrane.
8. The method of preparing an antimicrobial and anti-fouling microporous membrane according to claim 7, wherein the ultrasonic power of the ultrasonic treatment in step S1 is 200W; the organic solvent is any one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide.
9. The method for preparing the antibacterial and anti-pollution microporous membrane according to claim 7, wherein the mass ratio of the mixture to the methanol in the step S2 is 1 (5-8); the irradiation in the step S2 is performed at room temperature, the irradiation dose rate is 10-420 Gy/min, and the irradiation dose is 10-55 kGy.
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