CN114288880A - Antibacterial hydrophilic ultrafiltration membrane and preparation method thereof - Google Patents
Antibacterial hydrophilic ultrafiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of ultrafiltration membrane material preparation, and particularly relates to an antibacterial hydrophilic ultrafiltration membrane and a preparation method thereof; the method comprises the steps of introducing 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS) and quaternized carboxymethyl chitosan (QCTS) into an ultrafiltration membrane by adopting a physical and chemical modification combined method, introducing the QCTS into the ultrafiltration membrane in a blending mode to endow the ultrafiltration membrane with certain antibacterial performance, treating the membrane by using oxygen plasma to enable the surface of the membrane to generate active sites, grafting hydrophilic monomer DMAPS onto the surface of the ultrafiltration membrane under the simultaneous action of ultraviolet light and an initiator to endow the ultrafiltration membrane with better hydrophilic performance. The hydrophilic and antibacterial modification is carried out on the ultrafiltration membrane on the premise of high retention rate and high flux, and a new idea is provided for the technical field of ultrafiltration membranes.
Description
Technical Field
The invention belongs to the technical field of ultrafiltration membrane material preparation, and particularly relates to an antibacterial hydrophilic ultrafiltration membrane and a preparation method thereof.
Background
The ultrafiltration membrane is a polymer semipermeable membrane which can separate polymer colloid or suspended particles with certain size from a solution in the ultrafiltration process. The Ultrafiltration (UF) membrane has a pore diameter of 1-100nm, can separate substances with molecular weight of more than 1000Da in water body by the sieving action of the membrane pores, and is a low-pressure membrane filtration technology between Microfiltration (MF) and Nanofiltration (NF). The membrane pollution problem caused by the hydrophobicity of the material seriously restricts the application of the polysulfone ultrafiltration membrane.
The membrane pollution means that in the process of filtration, particles, colloids, microorganisms and the like in water are adsorbed and deposited on the surface of a membrane or in membrane pores due to mechanical action or physical and chemical interaction with an ultrafiltration membrane, so that the pore diameter of the membrane is reduced and even blocked, and finally the separation characteristic and the permeability of the membrane are continuously reduced, which is one of important problems to be solved urgently.
In the prior art, the approaches to mitigate membrane fouling are: (1) physical pretreatment means such as ultraviolet sterilization, sand filtration and membrane filtration; (2) physical and chemical pretreatment means such as flocculation, precipitation and the like; (3) chemical pretreatment means such as active chlorine, ozone, bactericide and the like; (4) and physically cleaning the surface of the membrane by using high-pressure water flow or circularly and chemically cleaning the surface of the membrane by using a reagent. (5) The membrane performance is improved by modifying the membrane.
Experience shows for a long time that the conventional means has complicated processes and high energy consumption and cost, the membrane pollution cannot be fundamentally solved, the treatment means such as chemical disinfection and the like can also act with ultrafiltration membrane materials to influence the separation performance and shorten the service life of the membrane, and the generated disinfection by-products are against the aim of environmental friendliness. The membrane modification is one of the relatively environmental-friendly and efficient methods at the present stage. There are two main types of membrane modification, one is physical modification and the other is chemical modification. The physical modification is mainly to realize the change of the membrane performance by blending the additives, has the advantages of simplicity, rapidness and relatively high efficiency, can directly and effectively change the membrane performance, but also has certain disadvantages, such as the reduction of the membrane performance caused by the compatibility problem of the additives and the membrane and the influence of the defects of the additives on the membrane performance.
The publication No. CN103495353B discloses a preparation method of a quaternized chitosan modified polysulfone ultrafiltration membrane, which is to modify the ultrafiltration membrane by directly blending quaternized chitosan and polysulfone, wherein in common quaternized chitosan, chitosan is a hydrophobic substance, and according to different quaternization degrees, the quaternized chitosan shows certain water solubility but is not completely dissolved in water, the hydrophilicity is relatively weaker, and the hydrophilic modification effect on the ultrafiltration membrane is possibly not obvious.
Patent document No. CN109569331B discloses a method for preparing a hydrophilic antibacterial filter membrane, which is to perform surface grafting modification treatment on a substrate filter membrane by using a modification solution prepared from an acrylamide monomer containing a guanidyl unit, a cross-linking agent, and a photoinitiator. According to the patent, an acrylamide monomer containing a guanidyl unit is introduced to the surface of a film, the monomer has certain hydrophilicity but relatively poor antibacterial performance, generally speaking, the surface antibacterial rate or the bactericidal rate of a plastic product is more than or equal to 90%, which indicates that the product has good antibacterial performance, according to the antibacterial performance test result in the patent embodiment, the bactericidal rate of the two kinds of bacteria is below 90%, and the antibacterial performance cannot reach the standard.
Patent document No. CN102698608B discloses a method for preparing an ultrafiltration membrane with permanent hydrophilicity and permanent antibacterial property, which comprises preparing a modifying solution from hydrophilic monomers such as acrylamide and acrylic acid containing capsaicin derivative structures and a photosensitizer, coating the modifying solution on the surface of the ultrafiltration membrane, and grafting and modifying by ultraviolet illumination. The patent adopts the ultraviolet grafting reaction directly on the surface of the ultrafiltration membrane, and the method has low grafting rate, low reaction efficiency and instability. The acrylamide monomer with a capsaicin derivative structure with a weak antibacterial effect is also selected as the antibacterial monomer in the patent, the bacteriostasis rate of staphylococcus aureus is below 90%, and the antibacterial performance does not reach the standard.
Disclosure of Invention
The invention provides an antibacterial hydrophilic ultrafiltration membrane and a preparation method thereof for solving the problems.
The method is realized by the following technical scheme:
1. an antimicrobial hydrophilic ultrafiltration membrane comprising: ultrafiltration basement membrane, initiator solution and grafting solution.
Furthermore, the ultrafiltration membrane is formed by using non-woven fabrics as a supporting material and reacting the casting solution with the supporting material by a liquid-solid phase conversion method.
Further, the casting solution is prepared by mixing polysulfone, quaternized carboxymethyl chitosan (QCTS) and N, N-Dimethylformamide (DMF) in a weight ratio of 16-21: 0.5-1: 78-83 in a mass ratio.
Further, the initiator solution is obtained by dissolving an initiator benzophenone in acetone; the mass percentage concentration of the initiator solution is 3.75-5.0 wt%.
Further, the grafting solution is an aqueous solution prepared from 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate, and the concentration is 0.2-0.3 g/mL.
Further, the monomer structural formula of the 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate is as follows:
further, the quaternized carboxymethyl chitosan (QCTS) has a structural formula:
2. the preparation method of the antibacterial hydrophilic ultrafiltration membrane comprises the following steps:
(1) preparing an ultrafiltration basement membrane: polysulfone, quaternized carboxymethyl chitosan (QCTS) and N, N-Dimethylformamide (DMF) were mixed at a ratio of 16-21: 0.5-1: 78-83, heating and stirring at 70-80 ℃ for 6-12h, uniformly mixing, and performing vacuum filtration for 2-4h to obtain a membrane casting solution; adopting non-woven fabrics as a supporting material, scraping the membrane casting solution on the non-woven fabrics by a scraper, and forming an ultrafiltration basal membrane by a liquid-solid phase conversion method;
furthermore, the thickness of the non-woven fabric supporting material is 3.2-3.5 mil.
Further, the liquid-solid phase conversion time is 0.5-1min, the temperature of the phase conversion water bath is 13-15 ℃, and the temperature of the hot washing water bath is 70-80 ℃.
Further, the thickness of the ultrafiltration membrane is 5.5-6 mil.
(2) Ultrasonic cleaning the ultrafiltration basement membrane in 25% alcohol solution for 10-12min at the ultrasonic frequency of 25-30kHz, naturally drying, treating for 5-7min by oxygen plasma at the radio frequency of 300-;
(3) and (3) placing the ultrafiltration membrane sample wafer obtained in the step (2) in a grafting solution, performing illumination for 2-4min by using an ultraviolet curing device, wherein the power of the ultraviolet curing device is 600-2000W, and the wavelength of ultraviolet light is 300-365nm, and then performing ultrasonic cleaning for 5-10min in an alcohol solution with the concentration of 50% to obtain the antibacterial hydrophilic ultrafiltration membrane.
In conclusion, the beneficial effects of the invention are as follows: the method adopts a method combining physical modification and chemical modification, introduces 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS) and quaternized carboxymethyl chitosan (QCTS) into an ultrafiltration membrane, introduces QCTS into the ultrafiltration membrane in a blending mode to endow the ultrafiltration membrane with certain antibacterial performance, treats the membrane with oxygen plasma to generate active sites on the surface of the membrane, grafts hydrophilic monomer DMAPS on the surface of the ultrafiltration membrane under the action of ultraviolet light and an initiator, and endows the ultrafiltration membrane with better hydrophilic performance. The hydrophilic and antibacterial modification is carried out on the ultrafiltration membrane on the premise of high retention rate and high flux, and a new idea is provided for the technical field of ultrafiltration membranes.
Through the introduction of the two monomers, the antibacterial performance and the hydrophilic performance of the ultrafiltration membrane are improved, so that the ultrafiltration membrane has certain resistance to membrane pollution on the premise of high flux and high rejection rate, and the service life of the ultrafiltration membrane is prolonged. The specific properties are as follows:
(1) the antibacterial hydrophilic ultrafiltration membrane provided by the invention has good performance in a water contact angle test, and the hydrophilic performance of the surface of the ultrafiltration membrane is improved and the water contact angle is reduced to 20.8 degrees from the original 95.5 degrees because the QCTS and the DMAPS both have carbonyl polar groups and the DMAPS both have sulfonic acid groups and have good hydrophilic performance.
(2) The antibacterial hydrophilic ultrafiltration membrane has good antibacterial performance on staphylococcus aureus and escherichia coli after two monomers are introduced, and the bacteriostasis rate of the antibacterial hydrophilic ultrafiltration membrane on two bacteria is over 90%.
Compared with the patent technology with the publication number of CN109569331B, the two monomers are adopted in the patent to simultaneously modify the hydrophilicity and the antibacterial property of the membrane surface, so that the strong hydrophilicity is given to the membrane surface, and the better antibacterial property is given to the membrane surface.
Compared with the patent technology with the publication number of CN102698608B, the conventional ultrafiltration membrane material is polysulfone or polyether sulfone, the two materials have stable surface properties and are not easy to generate chemical reaction. The method has the advantages that the oxygen plasma treatment is carried out on the surface of the ultrafiltration membrane, so that the surface of the ultrafiltration membrane generates hydroxyl, and then two monomers are grafted through ultraviolet light. The same that this patent antibiotic monomer chose for use is the acrylamide monomer of the weak capsaicin of antibiotic effect derived structure, and the antibacterial rate to staphylococcus aureus all is below 90%, and monomer for use relatively this patent, the quaternization carboxymethyl chitosan antibacterial property that this patent chooseed for use is stronger, and broader spectrum and antibacterial property are more lasting.
Drawings
FIG. 1 shows the result of the antibacterial performance test of the ultrafiltration membrane. Wherein (1) is staphylococcus aureus S.aureus, and (2) is escherichia coli E.coli; behavior a was a general ultrafiltration membrane, and behavior b was an antibacterial hydrophilic ultrafiltration membrane prepared in example 1.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
1. A preparation method of an antibacterial hydrophilic ultrafiltration membrane comprises the following steps:
(1) preparing an ultrafiltration basement membrane: dissolving 175g of polysulfone and 5g of quaternized carboxymethyl chitosan (QCTS) in DMF to prepare 1kg of bottom membrane casting solution, heating and stirring at 80 ℃ for 8h, uniformly mixing, carrying out vacuum filtration for 3h, and standing to obtain the casting solution;
adopting non-woven fabric as a supporting material, scraping the membrane casting solution on the non-woven fabric by using a scraper, adjusting the thickness to be 6mil, controlling a phase inversion water bath at 15 ℃ for 1min, and controlling a thermosetting water bath at 80 ℃ for 2min to form an ultrafiltration base membrane;
further, the thickness of the non-woven fabric support material is 3.0 mil.
(2) Weighing 1g of benzophenone by using an analytical balance, and dissolving the benzophenone in 20mL of acetone solution to obtain initiator solution;
and (2) ultrasonic cleaning the ultrafiltration basement membrane in 25% alcohol solution for 12min at the ultrasonic frequency of 25kHz, naturally drying, treating for 6min by adopting oxygen plasma, keeping the radio frequency power of 600W and the air inlet flow of 200mL/min in an initiator solution, sealing, placing in a water bath kettle at the temperature of 30 ℃ for storage for 2h, taking out, and naturally drying in a natural environment for 2h to obtain the ultrafiltration membrane sample.
(3) Weighing 6g of 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate by using an analytical balance, adding 20mL of water to obtain a grafted solution, namely a DMAPS solution, placing the ultrafiltration membrane sample obtained in the step (2) into the DMAPS solution, irradiating for 3min by using an ultraviolet curing device, wherein the power of the ultraviolet curing device is 600W, the wavelength of ultraviolet light is 365nm, placing the ultrafiltration membrane sample into 50% alcohol solution for ultrasonic cleaning for 5min, and removing unreacted monomers and an initiator to obtain the antibacterial hydrophilic ultrafiltration membrane with the DMAPS grafted surface, wherein the ultrasonic frequency is 25 kHz.
Comparative example 1
A preparation method of a hydrophilic modified ultrafiltration membrane comprises the following steps:
(1) preparing an ultrafiltration basement membrane: dissolving 180g of polysulfone in DMF to prepare 1kg of base membrane casting solution, heating and stirring at 80 ℃ for 8h, uniformly mixing, carrying out vacuum filtration for 3h, and standing to obtain the casting solution;
adopting non-woven fabric as a supporting material, scraping the membrane casting solution on the non-woven fabric by using a scraper, adjusting the thickness to be 6mil, controlling a phase inversion water bath at 15 ℃ for 1min, and controlling a thermosetting water bath at 80 ℃ for 2min to form an ultrafiltration base membrane;
(2) weighing 1g of benzophenone by using an analytical balance, and dissolving the benzophenone in 20mL of acetone solution to obtain initiator solution;
ultrasonic cleaning an ultrafiltration membrane in 25% alcohol solution for 12min at ultrasonic frequency of 25kHz, naturally drying, treating with oxygen plasma for 6min, radio frequency power of 600W and air inlet flow of 200mL/min, immediately adding into initiator solution, sealing, placing in a water bath kettle at 30 deg.C, storing for 2h, taking out, and naturally drying in natural environment for 2h to obtain an ultrafiltration membrane sample;
(3) weighing 6g of 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate by using an analytical balance, adding 20mL of water to obtain a grafted solution, namely a DMAPS solution, placing the ultrafiltration membrane sample obtained in the step (2) into the DMAPS solution, irradiating for 3min by using an ultraviolet curing device, wherein the power of the ultraviolet curing device is 600W, the wavelength of ultraviolet light is 365nm, placing the ultrafiltration membrane sample into 50% alcohol solution for ultrasonic cleaning for 5min, and removing unreacted monomers and an initiator to obtain the hydrophilic modified ultrafiltration membrane with the surface grafted DMAPS.
Comparative example 2
A preparation method of an antibacterial modified ultrafiltration membrane comprises the following steps:
(1) preparing an ultrafiltration basement membrane: dissolving 175g of polysulfone and 5g of quaternized carboxymethyl chitosan (QCTS) in DMF to prepare 1kg of bottom membrane casting solution, heating and stirring at 80 ℃ for 8h, uniformly mixing, carrying out vacuum filtration for 3h, and standing to obtain the casting solution;
and (3) adopting a non-woven fabric as a supporting material, scraping the membrane casting solution on the non-woven fabric by using a scraper, adjusting the thickness to be 6mil, controlling a phase inversion water bath at 15 ℃ for 1min, and controlling a thermosetting water bath at 80 ℃ for 2min to obtain the antibacterial modified ultrafiltration membrane.
Comparative example 3
The ultrafiltration membrane is prepared by adopting a conventional method and comprises the following steps:
(1) preparing an ultrafiltration basement membrane: dissolving 180g of polysulfone in DMF to prepare 1kg of base membrane casting solution, heating and stirring at 80 ℃ for 8h, uniformly mixing, carrying out vacuum filtration for 3h, and standing to obtain the casting solution;
and (3) adopting non-woven fabric as a supporting material, scraping the membrane casting solution on the non-woven fabric by using a scraper, adjusting the thickness to be 6mil, controlling a phase inversion water bath at 15 ℃ for 1min, and controlling a thermosetting water bath at 80 ℃ for 2min to obtain the conventional ultrafiltration membrane.
First, ultra-filtration membrane performance test
The ultrafiltration membranes prepared in example 1 and comparative examples 1 to 3 were subjected to the test of water contact angle, bacteriostatic rate, water flux and rejection rate, and the results are shown in table 1.
The water contact angle was measured by a water contact angle tester.
Testing water flux by membrane test bench, fixing the membrane in the membrane test bench, testing water flux of pure water at 30-40psi for 30min
BSA retention test: in a membrane test bench, raw water is prepared into a BSA solution with the concentration of 1800 plus 2400ppm, after running for 30min, produced water and raw water are respectively taken for TOC test, and the retention rate of BSA is calculated according to the TOC value, wherein the specific formula is as follows:
retention rate R (%) - (1-R produced water TOC/R raw water TOC). times.100%
Wherein, the TOC of the R produced water is the TOC value of the produced water, and the TOC of the R raw water is the TOC value of the raw water.
The antibacterial performance test method of the membrane is carried out according to the antibacterial performance test method of GB/T37206-2018 organic separation membrane
TABLE 1 Ultrafiltration Membrane Performance results
According to the test result, the modified antibacterial hydrophilic ultrafiltration membrane has good antibacterial performance and hydrophilicity, the modification has no influence on the flux of the ultrafiltration membrane and the retention rate of bovine serum albumin, and the ultrafiltration membrane is endowed with good antibacterial performance and hydrophilicity on the premise of ensuring the good flux and retention rate of the ultrafiltration membrane.
And (3) carrying out plate-laying test on the bacterial liquid after the ultrafiltration membrane before modification and the ultrafiltration membrane after modification are co-cultured with the bacterial liquid for 12h, and observing the growth condition of bacteria. From FIG. 1, it can be seen that the ultrafiltration membrane without grafted two monomers in row a still contains a large amount of bacteria after co-culturing with two bacterial solutions respectively. After the antibacterial hydrophilic ultrafiltration membrane prepared by the invention is respectively co-cultured with bacterial liquid, the bacterial quantity in the bacterial liquid is obviously reduced, wherein the bacteriostasis rate to staphylococcus aureus reaches 98%, and the bacteriostasis rate to escherichia coli reaches 91%.
Claims (8)
1. An antibacterial hydrophilic ultrafiltration membrane, characterized in that it comprises: ultrafiltration basement membrane, initiator solution and grafting solution;
the ultrafiltration basal membrane is formed by adopting non-woven fabric as a supporting material and reacting the membrane casting solution with the supporting material by a liquid-solid phase conversion method;
the initiator solution is obtained by dissolving an initiator benzophenone in acetone; the mass percentage concentration of the initiator solution is 3.75-5.0 wt%;
the grafting solution is an aqueous solution prepared from 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate, and the concentration is 0.2-0.3 g/mL.
2. The antimicrobial hydrophilic ultrafiltration membrane of claim 1, wherein the membrane casting solution is a mixture of polysulfone, quaternized carboxymethyl chitosan, and N, N-Dimethylformamide (DMF) in a weight ratio of 16-21: 0.5-1: 78-83 in a mass ratio.
3. The antimicrobial hydrophilic ultrafiltration membrane of claim 1, wherein said 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate has the monomer formula:
4. the antimicrobial hydrophilic ultrafiltration membrane of claim 2, wherein said quaternized carboxymethyl chitosan has the formula:
5. the preparation method of the antibacterial hydrophilic ultrafiltration membrane is characterized by comprising the following steps of:
(1) preparing an ultrafiltration basement membrane: polysulfone, quaternized carboxymethyl chitosan and N, N-dimethylformamide were mixed in a ratio of 16-21: 0.5-1: 78-83, heating and stirring at 70-80 ℃ for 6-12h, uniformly mixing, and performing vacuum filtration for 2-4h to obtain a membrane casting solution; adopting non-woven fabrics as a supporting material, scraping the membrane casting solution on the non-woven fabrics by a scraper, and forming an ultrafiltration basal membrane by a liquid-solid phase conversion method;
(2) ultrasonic cleaning the ultrafiltration membrane in 25% alcohol solution at ultrasonic frequency of 25-30kHz for 10-12min, naturally drying, treating with oxygen plasma for 5-7min, immediately adding into initiator solution, sealing, storing in 30 deg.C water bath kettle for 2 hr, and naturally drying for 1-2 hr to obtain ultrafiltration membrane sample;
(3) and (3) placing the ultrafiltration membrane sample wafer obtained in the step (2) in a grafting solution, performing illumination for 2-4min by using an ultraviolet curing device, wherein the power of the ultraviolet curing device is 600-2000W, and the wavelength of ultraviolet light is 300-365nm, and then performing ultrasonic cleaning for 5-10min in an alcohol solution with the concentration of 50% to obtain the antibacterial hydrophilic ultrafiltration membrane.
6. The method of claim 5, wherein the thickness of the nonwoven support material is 3.2-3.5 mil; the thickness of the ultrafiltration basement membrane is 5.5-6 mil.
7. The method for preparing the antibacterial hydrophilic ultrafiltration membrane according to claim 6, wherein the liquid-solid phase conversion time is 0.5-1min, the temperature of the phase conversion water bath is 13-15 ℃, and the temperature of the hot washing water bath is 70-80 ℃.
8. The method of claim 6, wherein the RF power of the oxygen plasma treatment is 300-600W, and the inlet gas flow is 100-200 mL/min.
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