CN110694477A - Antibacterial nanofiltration membrane and preparation method thereof - Google Patents
Antibacterial nanofiltration membrane and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Abstract
The invention provides a preparation method of an antibacterial nanofiltration membrane, which is characterized by comprising the following steps: preparing vinyl tubular nano ZnO, (II) preparing a vinyl tubular nano ZnO end-capped thiazole-based polymer base material, (III) preparing a base membrane, and (IV) forming a nanofiltration membrane. The invention also provides the antibacterial nanofiltration membrane prepared by the preparation method of the antibacterial nanofiltration membrane. The antibacterial nanofiltration membrane provided by the invention has the advantages of obvious antibacterial effect, excellent mechanical property, high membrane flux and strong pollution resistance.
Description
Technical Field
The invention relates to the technical field of nanofiltration membranes, in particular to an antibacterial nanofiltration membrane and a preparation method thereof.
Background
In recent years, with the development of economy and the promotion of global industrialization progress, the problem of water pollution is increasingly severe, the national environmental protection policy puts more and more strict requirements and limits on the treatment of polluted wastewater, and the wastewater treatment and the efficient recycling become the problems which the wastewater discharge enterprises have to face. The nanofiltration membrane separation technology is one of the important means for wastewater reuse, is a pressure-driven membrane separation technology, has the characteristics of low operation pressure, low energy consumption, low equipment cost and the like, and is widely applied to the fields of seawater desalination, wastewater treatment, drinking water purification, food, medicine and the like.
The nanofiltration membrane is an essential material in the nanofiltration membrane separation technology, is also called as a loose reverse osmosis membrane, is a novel separation membrane with the pore diameter between the reverse osmosis membrane and an ultrafiltration membrane, has the nanoscale membrane pore diameter, is provided with multiple charges on the membrane, allows low molecular salt to pass through and then intercepts organic matters and multivalent ions with higher molecular weight, and has unique separation performance and higher separation precision. The performance of the separator directly influences the separation effect, and further influences the wastewater treatment and recovery. Therefore, it is important to develop a nanofiltration membrane with excellent performance.
Antibacterial properties are an important criterion for measuring the performance of nanofiltration membranes. Microorganisms and bacteria in the wastewater can be deposited and propagated on the nanofiltration membrane in the using process of the nanofiltration membrane to form a biofilm, so that the nanofiltration membrane is polluted, the membrane flux is reduced rapidly, the service life of the nanofiltration membrane is further shortened, and the wastewater treatment and recovery cost is increased. The development of the nanofiltration membrane with excellent antibacterial performance is the mainstream trend of the development of the nanofiltration membrane industry at the present stage and in some time in the future. In addition, nanofiltration membrane raw materials in the prior art such as PVDF (polyvinylidene fluoride), PSF (polysulfone) or Polyethersulfone (PES) are linear polymers, and the distance between molecular chains is large, so that the desalting effect is poor. Although a body-type structure can be formed by crosslinking, the hydrophilicity of the material has great influence on the flux and the anti-pollution performance of the membrane, and after the functional groups of the hydrophilic crosslinking monomer are crosslinked, the functional groups are consumed, so that the hydrophilicity of the membrane, the flux of the membrane and the anti-pollution performance are reduced.
Chinese patent CN101874989A prepares a polyamide thin-layer composite membrane on a polysulfone support layer by interfacial polymerization, and then adds an aqueous solution of inorganic nanoparticles containing silver, copper, zinc and corresponding compounds on the polyamide surface layer to prepare a second polyamide surface layer containing antibacterial inorganic nanoparticles as an antibacterial functional layer. The antibacterial nanofiltration membrane prepared by the method has good antibacterial property, but antibacterial particles are easy to run off in the use process of the membrane, the antibacterial durability of the nanofiltration membrane is poor, and the selective permeability of the antibacterial composite nanofiltration membrane is not good.
Therefore, it is necessary to develop an antibacterial nanofiltration membrane with remarkable antibacterial effect, excellent mechanical properties, high membrane flux and strong pollution resistance.
Disclosure of Invention
The invention mainly aims to provide an antibacterial nanofiltration membrane which has the advantages of remarkable antibacterial effect, excellent mechanical property, high membrane flux and strong pollution resistance. Meanwhile, the invention also provides a preparation method of the antibacterial nanofiltration membrane.
In order to achieve the above purpose, the invention provides a preparation method of an antibacterial nanofiltration membrane, which comprises the following steps:
preparing vinyl tubular nano ZnO: dispersing tubular nano ZnO in an organic solvent, adding a silane coupling agent KH550, stirring and reacting for 4-6 hours at 60-80 ℃, centrifuging, washing for 3-5 times by using ethanol, and drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain vinyl tubular nano ZnO;
(II) preparation of vinyl tubular nano ZnO end-capped thiazole-based polymer substrate: adding 2,2' -diallyl bisphenol A, 4-amino-4H-1, 2, 4-thiazole-3, 5-dithiol and a catalyst into a high-boiling-point solvent, stirring and reacting for 13-18 hours at the temperature of 110 ℃ and 130 ℃ under the atmosphere of nitrogen or inert gas, then adding the vinyl tubular nano ZnO prepared in the step (I), continuing to perform heat preservation and reaction for 2-4 hours, after the reaction is finished, precipitating a polymer in water, washing the product for 3-5 times by using ethanol, and then drying the product in a vacuum drying box at the temperature of 80-90 ℃ to constant weight to obtain a vinyl tubular nano ZnO terminated thiazole-based polymer substrate;
(III) preparation of a base film: adding the vinyl tubular nano ZnO end-capped thiazole-based polymer base material prepared in the step (II) into a dispersion solvent to form a dispersion solution, filtering the dispersion solution by using a polytetrafluoroethylene filter membrane with the aperture of 0.1-0.3 mu m, and then defoaming in vacuum to obtain a membrane casting solution; scraping the casting solution on a substrate with a smooth surface to form a thin-layer liquid film; after the solvent in the thin-layer liquid film is volatilized for a certain time, immersing the thin-layer liquid film into a hydrogel bath at the temperature of 20-25 ℃ for phase conversion to form a film, and obtaining a base film;
(IV) forming a nanofiltration membrane: and (3) immersing the base membrane prepared in the step (three) into a 0.5-1% alginic acid solution for 1-2 hours, taking out, drying at the constant temperature of 50-80 ℃, rinsing with deionized water, and taking out to obtain the antibacterial nanofiltration membrane.
Further, in the step (I), the mass ratio of the tubular nano ZnO to the organic solvent to the silane coupling agent KH550 is (3-5): (10-16): 0.5-1.
Preferably, the organic solvent is selected from at least one of ethanol, dichloromethane, tetrahydrofuran, and N, N-dimethylformamide.
Furthermore, in the step (II), the mass ratio of the 2,2' -diallyl bisphenol A, the 4-amino-4H-1, 2, 4-thiazole-3, 5-dithiol, the catalyst, the high-boiling-point solvent and the vinyl tubular nano ZnO is 2:1 (0.3-0.6) to 0.2 (10-15).
Preferably, the catalyst is at least one of sodium ethoxide, sodium hydride, sodium amide and potassium tert-butyl alkoxide; the high boiling point solvent is at least one selected from dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is at least one of helium, neon and argon.
Further, the mass ratio of the vinyl tubular nano ZnO end capping based on the thiazole polymer base material and the dispersing solvent in the step (III) is 1 (6-10).
Preferably, the dispersing solvent is one selected from tetrahydrofuran, N-dimethylformamide and chloroform; the certain time is 1-3 hours.
Further, the mass ratio of the basement membrane to the alginic acid solution in the step (IV) is 1 (10-20).
Further, the antibacterial nanofiltration membrane is prepared according to the preparation method of the antibacterial nanofiltration membrane.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the antibacterial nanofiltration membrane disclosed by the invention has the advantages of simple preparation method and process, easiness in operation, capability of meeting the requirements of large-scale production, low requirements on equipment and reaction conditions, easiness in obtaining of raw materials, low cost, safety and environmental friendliness in the preparation process, and higher popularization and application values.
(2) The antibacterial nanofiltration membrane disclosed by the invention overcomes the technical problems that the traditional nanofiltration membrane has poor desalting effect due to large space between molecular chains, does not have antibacterial performance, and the hydrophilicity, flux and anti-pollution performance of the membrane need to be further improved, and also overcomes the defects that antibacterial particles of the antibacterial nanofiltration membrane in the prior art are easy to lose in the use process of the membrane, the antibacterial durability of the nanofiltration membrane is poor, and the selective permeability of the antibacterial composite nanofiltration membrane is not good.
(3) According to the antibacterial nanofiltration membrane disclosed by the invention, the main chain of the basic membrane molecule is formed by condensation polymerization of micromolecules containing phenol groups and thiazolyl through a click reaction to form a condensation polymer containing phenol groups and thiazole groups on the main chain of the molecule, and the two structures have synergistic effect and can obviously improve the antibacterial performance; the vinyl tubular nano ZnO is used for sealing the end, on one hand, a tubular nano ZnO structure is introduced, the tubular nano structure of the structure has extremely high transmission performance and high chemical selectivity, the atomically smooth inner surface of the tubular nano ZnO can greatly reduce the adsorption force and the friction force when fluid passes through, and in addition, the aperture of the tubular nano ZnO can be continuously adjusted in a nano scale, so that the accurate control of the aperture of the nano-filtration membrane is facilitated, and the nano-filtration membrane taking the tubular nano ZnO as a transport channel can simultaneously obtain high permeation rate and high selectivity; the antibacterial property can be further improved by adding the nano zinc oxide, and the nano zinc oxide is connected with a molecular chain by a chemical bond, so that the dispersibility and the compatibility are better; on the other hand, the end capping is carried out on the polycondensate, the terminated chain continues to grow, and the molecular weight distribution of the molecular structure of the base film are effectively controlled, so that the comprehensive performance of the base film is improved.
(4) According to the antibacterial nanofiltration membrane disclosed by the invention, after the base membrane is prepared, the surface of the base membrane is crosslinked by alginic acid, and meanwhile, an active hydrophilic hydroxyl structure is introduced, so that the comprehensive performance of the nanofiltration membrane can be effectively improved, the surface hydrophilicity of the membrane is improved, and the flux and the pollution resistance of the membrane are preferably improved; and secondly, the introduction of the natural high molecular polymer alginic acid can also be used for improving the antibacterial property of the nanofiltration membrane by synergistic action with other functional components.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
In the embodiment of the invention, the tubular nano ZnO is prepared in advance, and the preparation method refers to the following steps: hydrothermal synthesis and field emission characteristic study of tubular ZnO nanostructures, king jade, university of east china, 2008; other related raw materials were purchased commercially.
Example 1
A preparation method of an antibacterial nanofiltration membrane comprises the following steps:
preparing vinyl tubular nano ZnO: dispersing 30g of tubular nano ZnO in 100g of ethanol, adding a silane coupling agent KH5505g, stirring at 60 ℃ for reacting for 4 hours, centrifuging, washing with ethanol for 3 times, and drying in a vacuum drying oven at 80 ℃ to constant weight to obtain vinyl tubular nano ZnO;
(II) preparation of vinyl tubular nano ZnO end-capped thiazole-based polymer substrate: adding 10g of 2,2' -diallyl bisphenol A20g, 4-amino-4H-1, 2, 4-thiazole-3, 5-dithiol and 3g of sodium ethoxide into 100g of dimethyl sulfoxide, stirring and reacting at 110 ℃ for 13 hours under the nitrogen atmosphere, then adding 2g of vinyl tubular nano ZnO prepared in the step (I), continuing to perform heat preservation reaction for 2 hours, precipitating a polymer in water after the reaction is finished, washing the product for 3 times with ethanol, and drying in a vacuum drying oven at 80 ℃ to constant weight to obtain a vinyl tubular nano ZnO terminated thiazole-based polymer substrate;
(III) preparation of a base film: adding 10g of the vinyl tubular nano ZnO end-capped thiazole-based polymer base material prepared in the step (II) into 60g of tetrahydrofuran to form a dispersion solution, filtering the dispersion solution by using a polytetrafluoroethylene filter membrane with the aperture of 0.1 mu m, and then defoaming in vacuum to obtain a membrane casting solution; scraping the casting solution on a substrate with a smooth surface to form a thin-layer liquid film; after the solvent in the thin liquid film is volatilized for 1 hour, the thin liquid film is immersed into a hydrogel bath at the temperature of 20 ℃ to be converted into a film, and a basement film is obtained;
(IV) forming a nanofiltration membrane: and (3) immersing 10g of the base membrane prepared in the step (three) into 100g of alginic acid solution with the mass fraction of 0.5% for 1 hour, then taking out, drying at the constant temperature of 50 ℃, rinsing with deionized water, and taking out to obtain the antibacterial nanofiltration membrane.
An antibacterial nanofiltration membrane is prepared according to the preparation method of the antibacterial nanofiltration membrane.
Example 2
A preparation method of an antibacterial nanofiltration membrane comprises the following steps:
preparing vinyl tubular nano ZnO: dispersing 35g of tubular nano ZnO in 120g of dichloromethane, adding a silane coupling agent KH5506g, stirring at 65 ℃ for reacting for 4.5 hours, centrifuging, washing with ethanol for 4 times, and drying in a vacuum drying oven at 83 ℃ to constant weight to obtain vinyl tubular nano ZnO;
(II) preparation of vinyl tubular nano ZnO end-capped thiazole-based polymer substrate: adding 10g of 2,2' -diallyl bisphenol A20g, 4-amino-4H-1, 2, 4-thiazole-3, 5-dithiol and 4g of sodium hydride into 110g of N, N-dimethylformamide, stirring and reacting for 14.5 hours at 115 ℃ under the atmosphere of helium, then adding 2g of vinyl tubular nano ZnO prepared in the step (I), continuing to perform heat preservation reaction for 2.5 hours, precipitating a polymer in water after the reaction is finished, washing the product for 4 times by using ethanol, and drying in a vacuum drying oven at 83 ℃ to constant weight to obtain a vinyl tubular nano ZnO terminated thiazole-based polymer substrate;
(III) preparation of a base film: adding 10g of the vinyl tubular nano ZnO end-capped thiazole-based polymer base material prepared in the step (II) into 70g of N, N-dimethylformamide to form a dispersion solution, filtering the dispersion solution by using a polytetrafluoroethylene filter membrane with the aperture of 0.2 mu m, and then defoaming in vacuum to obtain a membrane casting solution; scraping the casting solution on a substrate with a smooth surface to form a thin-layer liquid film; after the solvent in the thin liquid film is volatilized for 1.5 hours, the thin liquid film is immersed into a hydrogel bath at the temperature of 21 ℃ to be converted into a film, and a basement film is obtained;
(IV) forming a nanofiltration membrane: and (3) immersing 10g of the base membrane prepared in the step (three) into 120g of alginic acid solution with the mass fraction of 0.6% for 1.2 hours, then taking out, drying at the constant temperature of 60 ℃, rinsing with deionized water, and taking out to obtain the antibacterial nanofiltration membrane.
An antibacterial nanofiltration membrane is prepared according to the preparation method of the antibacterial nanofiltration membrane.
Example 3
A preparation method of an antibacterial nanofiltration membrane comprises the following steps:
preparing vinyl tubular nano ZnO: dispersing 40g of tubular nano ZnO in 135g of tetrahydrofuran, adding 7.5g of silane coupling agent KH5507, stirring at 70 ℃ for reaction for 5 hours, centrifuging, washing with ethanol for 4 times, and drying in a vacuum drying oven at 85 ℃ to constant weight to obtain vinyl tubular nano ZnO;
(II) preparation of vinyl tubular nano ZnO end-capped thiazole-based polymer substrate: adding 10g of 2,2' -diallyl bisphenol A20g, 4-amino-4H-1, 2, 4-thiazole-3, 5-dithiol and 5g of sodium amide into 135g of N, N-dimethylacetamide, stirring and reacting at 120 ℃ for 15 hours under the atmosphere of neon, then adding 2g of vinyl tubular nano ZnO prepared in the step (I), continuing to perform heat preservation reaction for 3 hours, precipitating a polymer in water after the reaction is finished, washing the product with ethanol for 4 times, and drying in a vacuum drying oven at 85 ℃ to constant weight to obtain a vinyl tubular nano ZnO terminated thiazole-based polymer substrate;
(III) preparation of a base film: adding 10g of the vinyl tubular nano ZnO end-capped thiazole-based polymer base material prepared in the step (II) into 80g of chloroform to form a dispersion solution, filtering the dispersion solution by using a polytetrafluoroethylene filter membrane with the aperture of 0.2 mu m, and performing vacuum defoaming to obtain a membrane casting solution; scraping the casting solution on a substrate with a smooth surface to form a thin-layer liquid film; after the solvent in the thin-layer liquid film is volatilized for 2 hours, the thin-layer liquid film is immersed into a hydrogel bath at the temperature of 23 ℃ to be converted into a film, and a basement film is obtained;
(IV) forming a nanofiltration membrane: and (3) immersing 10g of the base membrane prepared in the step (three) into 150g of alginic acid solution with the mass fraction of 0.7% for 1.5 hours, then taking out, drying at the constant temperature of 65 ℃, rinsing with deionized water, and taking out to obtain the antibacterial nanofiltration membrane.
An antibacterial nanofiltration membrane is prepared according to the preparation method of the antibacterial nanofiltration membrane.
Example 4
A preparation method of an antibacterial nanofiltration membrane comprises the following steps:
preparing vinyl tubular nano ZnO: dispersing 45g of tubular nano ZnO in 150g of organic solvent, adding a silane coupling agent KH5509g, stirring at 75 ℃ for reaction for 5.5 hours, centrifuging, washing with ethanol for 4.8 times, and drying in a vacuum drying oven at 88 ℃ to constant weight to obtain vinyl tubular nano ZnO; the organic solvent is formed by mixing ethanol, dichloromethane, tetrahydrofuran and N, N-dimethylformamide according to the mass ratio of 1:2:2: 3;
(II) preparation of vinyl tubular nano ZnO end-capped thiazole-based polymer substrate: adding 10g of 2,2' -diallyl bisphenol A20g, 4-amino-4H-1, 2, 4-thiazole-3, 5-dithiol and 5.5g of catalyst into 145g of high-boiling-point solvent, stirring and reacting for 17 hours at 125 ℃ under the argon atmosphere, then adding 2g of vinyl tubular nano ZnO prepared in the step (I), continuing to perform heat preservation reaction for 3.8 hours, precipitating a polymer in water after the reaction is finished, washing the product for 4 times with ethanol, and drying in a vacuum drying oven at 88 ℃ to constant weight to obtain a vinyl tubular nano ZnO terminated thiazole-based polymer substrate; the catalyst is formed by mixing sodium ethoxide, sodium hydride, sodium amide and tert-butyl potassium alcoholate according to the mass ratio of 1:2:1: 1; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:2:2: 3;
(III) preparation of a base film: adding 10g of the vinyl tubular nano ZnO end-capped thiazole-based polymer base material prepared in the step (II) into 90g of tetrahydrofuran to form a dispersion solution, filtering the dispersion solution by using a polytetrafluoroethylene filter membrane with the aperture of 0.2 mu m, and then defoaming in vacuum to obtain a membrane casting solution; scraping the casting solution on a substrate with a smooth surface to form a thin-layer liquid film; after the solvent in the thin-layer liquid film is volatilized for 2.5 hours, the thin-layer liquid film is immersed into a hydrogel bath at the temperature of 23 ℃ to be converted into a film, and a basement film is obtained;
(IV) forming a nanofiltration membrane: and (3) immersing 10g of the base membrane prepared in the step (three) into 180g of alginic acid solution with the mass fraction of 0.8% for 1.5 hours, then taking out, drying at the constant temperature of 70 ℃, rinsing with deionized water, and taking out to obtain the antibacterial nanofiltration membrane.
An antibacterial nanofiltration membrane is prepared according to the preparation method of the antibacterial nanofiltration membrane.
Example 5
A preparation method of an antibacterial nanofiltration membrane comprises the following steps:
preparing vinyl tubular nano ZnO: dispersing 50g of tubular nano ZnO in 160g of tetrahydrofuran, adding a silane coupling agent KH55010g, stirring at 80 ℃ for reacting for 6 hours, centrifuging, washing with ethanol for 5 times, and drying in a vacuum drying oven at 90 ℃ to constant weight to obtain vinyl tubular nano ZnO;
(II) preparation of vinyl tubular nano ZnO end-capped thiazole-based polymer substrate: adding 10g of 2,2' -diallyl bisphenol A20g, 4-amino-4H-1, 2, 4-thiazole-3, 5-dithiol and 6g of potassium tert-butyl alkoxide into 150g of N-methylpyrrolidone, stirring and reacting at 130 ℃ for 18 hours under the nitrogen atmosphere, then adding 2g of vinyl tubular nano ZnO prepared in the step (I), continuing to perform heat preservation and reacting for 4 hours, precipitating a polymer in water after the reaction is finished, washing the product with ethanol for 5 times, and drying in a vacuum drying oven at 90 ℃ to constant weight to obtain a vinyl tubular nano ZnO terminated thiazole-based polymer substrate;
(III) preparation of a base film: adding 10g of the vinyl tubular nano ZnO end-capped thiazole-based polymer base material prepared in the step (II) into 100g of chloroform to form a dispersion solution, filtering the dispersion solution by using a polytetrafluoroethylene filter membrane with the aperture of 0.3 mu m, and performing vacuum defoaming to obtain a membrane casting solution; scraping the casting solution on a substrate with a smooth surface to form a thin-layer liquid film; after the solvent in the thin-layer liquid film is volatilized for 3 hours, the thin-layer liquid film is immersed into a hydrogel bath at 25 ℃ to be phase-converted into a film, and a basement film is obtained;
(IV) forming a nanofiltration membrane: and (3) immersing 10g of the base membrane prepared in the step (three) into 1% by mass of alginic acid solution for 200g of 2 hours, taking out, drying at the constant temperature of 80 ℃, rinsing with deionized water, and taking out to obtain the antibacterial nanofiltration membrane.
An antibacterial nanofiltration membrane is prepared according to the preparation method of the antibacterial nanofiltration membrane.
Comparative example 1
The formula and preparation method of the antibacterial nanofiltration membrane are the same as those of example 1, except that the vinyl tubular nano ZnO end capping is not used in the preparation process of the thiazole polymer base material.
Comparative example 2
The formula and the preparation method of the antibacterial nanofiltration membrane are the same as those of the example 1, except that the step (IV) of soaking the alginic acid solution is omitted.
Comparative example 3
Commercial antibacterial nanofiltration membranes.
The antibacterial nanofiltration membranes described in examples 1-5 and comparative examples 1-3 were subjected to performance tests, and the test results and test methods are shown in table 1.
Table 1 antibacterial nanofiltration membrane performance test results
As can be seen from table 1, the antibacterial nanofiltration membrane disclosed in the embodiment of the present invention has a higher pure water flux, a higher salt rejection rate, and a better antibacterial performance than commercially available products.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The preparation method of the antibacterial nanofiltration membrane is characterized by comprising the following steps:
preparing vinyl tubular nano ZnO: dispersing tubular nano ZnO in an organic solvent, adding a silane coupling agent KH550, stirring and reacting for 4-6 hours at 60-80 ℃, centrifuging, washing for 3-5 times by using ethanol, and drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain vinyl tubular nano ZnO;
(II) preparation of vinyl tubular nano ZnO end-capped thiazole-based polymer substrate: adding 2,2' -diallyl bisphenol A, 4-amino-4H-1, 2, 4-thiazole-3, 5-dithiol and a catalyst into a high-boiling-point solvent, stirring and reacting for 13-18 hours at the temperature of 110 ℃ and 130 ℃ under the atmosphere of nitrogen or inert gas, then adding the vinyl tubular nano ZnO prepared in the step (I), continuing to perform heat preservation and reaction for 2-4 hours, after the reaction is finished, precipitating a polymer in water, washing the product for 3-5 times by using ethanol, and then drying the product in a vacuum drying box at the temperature of 80-90 ℃ to constant weight to obtain a vinyl tubular nano ZnO terminated thiazole-based polymer substrate;
(III) preparation of a base film: adding the vinyl tubular nano ZnO end-capped thiazole-based polymer base material prepared in the step (II) into a dispersion solvent to form a dispersion solution, filtering the dispersion solution by using a polytetrafluoroethylene filter membrane with the aperture of 0.1-0.3 mu m, and then defoaming in vacuum to obtain a membrane casting solution; scraping the casting solution on a substrate with a smooth surface to form a thin-layer liquid film; after the solvent in the thin-layer liquid film is volatilized for a certain time, immersing the thin-layer liquid film into a hydrogel bath at the temperature of 20-25 ℃ for phase conversion to form a film, and obtaining a base film;
(IV) forming a nanofiltration membrane: and (3) immersing the base membrane prepared in the step (three) into a 0.5-1% alginic acid solution for 1-2 hours, taking out, drying at the constant temperature of 50-80 ℃, rinsing with deionized water, and taking out to obtain the antibacterial nanofiltration membrane.
2. The method for preparing an antibacterial nanofiltration membrane according to claim 1, wherein the mass ratio of the tubular nano ZnO, the organic solvent and the silane coupling agent KH550 in the step (I) is (3-5): (10-16): (0.5-1).
3. The method for preparing an antibacterial nanofiltration membrane according to claim 1, wherein the organic solvent is at least one selected from ethanol, dichloromethane, tetrahydrofuran and N, N-dimethylformamide.
4. The method for preparing an antibacterial nanofiltration membrane according to claim 1, wherein in the step (II), the mass ratio of the 2,2' -diallyl bisphenol A, the 4-amino-4H-1, 2, 4-thiazole-3, 5-dithiol, the catalyst, the high-boiling-point solvent and the vinyl tubular nano ZnO is 2:1 (0.3-0.6) to 0.2 (10-15).
5. The method for preparing an antibacterial nanofiltration membrane according to claim 1, wherein the catalyst is at least one of sodium ethoxide, sodium hydride, sodium amide and potassium tert-butoxide; the high boiling point solvent is at least one selected from dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is at least one of helium, neon and argon.
6. The preparation method of the antibacterial nanofiltration membrane of claim 1, wherein in the step (III), the mass ratio of the vinyl tubular nano ZnO terminated end based on the thiazole polymer substrate to the dispersion solvent is 1 (6-10).
7. The method for preparing an antibacterial nanofiltration membrane according to claim 1, wherein the dispersion solvent is one selected from tetrahydrofuran, N-dimethylformamide and chloroform; the certain time is 1-3 hours.
8. The method for preparing an antibacterial nanofiltration membrane according to claim 1, wherein the mass ratio of the basement membrane to the alginic acid solution in the step (IV) is 1 (10-20).
9. An antibacterial nanofiltration membrane prepared by the preparation method of the antibacterial nanofiltration membrane of any one of claims 1 to 8.
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| CN112521597A (en) * | 2020-11-25 | 2021-03-19 | 吉林大学 | Sulfhydryl-containing polyarylether compound, preparation method and application thereof, antibacterial ultrafiltration membrane and preparation method thereof |
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