CN112237853A - Antibacterial and anti-pollution microporous membrane and preparation method thereof - Google Patents
Antibacterial and anti-pollution microporous membrane and preparation method thereof Download PDFInfo
- Publication number
- CN112237853A CN112237853A CN202010970029.8A CN202010970029A CN112237853A CN 112237853 A CN112237853 A CN 112237853A CN 202010970029 A CN202010970029 A CN 202010970029A CN 112237853 A CN112237853 A CN 112237853A
- Authority
- CN
- China
- Prior art keywords
- pollution
- antibacterial
- membrane
- microporous membrane
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- 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
-
- 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
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an antibacterial and anti-pollution microporous membrane and a preparation method thereof. The antibacterial and anti-pollution microporous membrane consists of an antibacterial and anti-pollution separation layer and a supporting layer, wherein the antibacterial and anti-pollution separation layer contains an antibacterial component and an anti-pollution component, the antibacterial component and the anti-pollution component are connected through a carbon-carbon bond, and the supporting layer consists of a membrane matrix material and a copolymer containing tertiary amine. The anti-pollution component is formed by copolymerizing an anti-pollution monomer and a reactive monomer containing benzyl halide. The invention further discloses a preparation method of the antibacterial and anti-pollution microporous membrane. The antibacterial and anti-pollution microporous membrane can simultaneously realize the flux recovery rate of more than 95 percent and the bacteria killing rate of more than 99 percent, and endows the microporous membrane with antibacterial and anti-pollution functions. The microporous membrane can be applied to the fields of sewage treatment, tap water purification, food industry, seawater desalination pretreatment, biomedicine and the like.
Description
Technical Field
The invention belongs to the scientific and technical field of water treatment and membrane separation, and particularly relates to an antibacterial and anti-pollution microporous membrane and a preparation method thereof.
Background
The membrane separation technology has the advantages of high separation efficiency, small occupied area, low energy consumption, simple and convenient operation and the like, and becomes one of the most important means in the separation science at present. The problem of membrane fouling has plagued more profound developments in polymer membrane separation technology. In particular, during the operation, the adhesion and growth of bacteria in the feed liquid on the membrane surface cause the membrane flux to be reduced sharply, the separation performance is damaged, and the application of the membrane separation technology in many industrial aspects is limited.
There are some reports related to the modification of polymer separation membranes to resist bacteria and pollution. For example, patent CN104524986A discloses a hydrophilic antibacterial membrane prepared by immersing a basement membrane in a dopamine solution, forming a polydopamine layer on the surface of the basement membrane by self-polymerization of dopamine, reacting with a polyethyleneimine aqueous solution, and finally performing a cationization reaction. In the invention patent CN104190274A, a silver nanoparticle zwitterionic polymer brush is prepared by taking polyvinylidene fluoride, silver ions and a zwitterionic monomer as main raw materials and is grafted on the surface of a polyvinylidene fluoride membrane to achieve the aim of antibiosis. According to the invention patent CN105727773B, quaternary ammonium salt is blended in a film-forming polymer and an additive, and a membrane is prepared by an immersion precipitation phase inversion method, so that a quaternary ammonium salt-containing modified polymer separation membrane can be obtained. The invention patent CN107670506A immerses the PVDF microporous membrane obtained by phase conversion in a silver-loaded chitosan film forming solution for surface coating and drying to prepare the hydrophilic antibacterial pollution-resistant PVDF microporous membrane. In the invention patent CN109260965A, after polymerization grafting is initiated on the surface of a PVDF membrane by plasma, zwitterions are generated by one-step reaction to prepare the anti-pollution membrane. In patent CN 108927018A, a polysulfone-based membrane is soaked in a m-phenylenediamine solution, a trimesoyl chloride solution, a polyethyleneimine solution and a nano silver colloid at one time to prepare the anti-pollution antibacterial forward osmosis membrane. However, in the above modification method, the antibacterial layer and the anti-pollution layer are made of the same material, so that the optimal effects of both antibacterial and anti-pollution cannot be obtained, and the modified layer is easy to desorb to cause the loss of the anti-pollution capability, so that the problem of membrane pollution in the long-term use process of the separation membrane cannot be solved. For example, the literature (desalinization, 2013, 324: 48-56) reports that silver nanoparticle modified ultrafiltration membranes are formed in situ, and have antibacterial and anti-pollution properties, but it is also found in research that nano silver is gradually lost in the form of silver ions. The gradual disappearance of the effective antimicrobial anti-fouling components affects the long-term performance of the membrane.
The quaternary ammonium salt as a broad-spectrum bactericide has the characteristics of high efficiency, low toxicity, difficult influence of pH value change, stable chemical performance and the like. The amphoteric ion polymer is a polymer containing both positive and negative ion groups, and combines water molecules through the electrostatic force between the positive and negative ion groups to form a stable hydration layer, thereby effectively preventing or reducing the contact between membrane pollutants and the surface of the membrane. Polyethylene glycol is a common hydrophilic substance and is used for hydrophilization and anti-pollution modification of a polymer separation membrane. Therefore, the broad-spectrum bactericidal performance of the quaternary ammonium salt and the anti-pollution performance of the zwitterionic polymer or the polyethylene glycol are combined at the same time, and the quaternary ammonium salt is stably combined on the surface of the separation membrane, so that the method has important significance.
Disclosure of Invention
In order to solve the pollution problem of long-term use of the membrane in the prior membrane separation technology, the invention prepares an antibacterial and anti-pollution microporous membrane by an antibacterial component and an anti-pollution component which are connected by a carbon-carbon bond
The invention aims to prepare a microporous membrane with antibacterial and anti-pollution functions. On one hand, the microporous membrane realizes a long-term anti-pollution effect and prevents pollutants from being adsorbed; on the other hand, the composite can effectively kill bacteria, inhibit the growth and adhesion of microorganisms and synergistically promote the anti-pollution performance of the microporous membrane.
The antibacterial and anti-pollution microporous membrane provided by the invention consists of an antibacterial and anti-pollution separation layer and a support layer, wherein the antibacterial and anti-pollution separation layer contains an antibacterial component and an anti-pollution component, the antibacterial component and the anti-pollution component are connected through a carbon-carbon bond, and the support layer consists of a membrane matrix material and a copolymer containing tertiary amine. The antibacterial component is generated by quaternary amination reaction of amphiphilic copolymer containing tertiary amine and reactable monomer containing benzyl halide, and the anti-pollution component is formed by copolymerization of anti-pollution monomer and reactable monomer containing benzyl halide.
The antibacterial component is generated by carrying out quaternization reaction on an amphiphilic copolymer containing tertiary amine and a reactable monomer containing benzyl halide, wherein the amphiphilic copolymer containing the tertiary amine is obtained by copolymerizing a monomer containing the tertiary amine and a hydrophobic monomer; the tertiary amine-containing monomer is selected from one or more of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, 4-vinylpyridine, 2-vinylpyridine and vinylimidazole; the hydrophobic monomer is selected from any one or more of methyl methacrylate, methyl acrylate, styrene, vinyl chloride, trifluoroethyl methacrylate, perfluorooctyl methacrylate, trifluoroethyl acrylate and perfluorooctyl acrylate; the reactive monomer containing benzyl halide (Cl and Br) has the following structural formula:
wherein: x is selected from Cl or Br.
The anti-pollution component is formed by copolymerization of anti-pollution monomers and reactable monomers containing benzyl halides (Cl and Br), wherein the anti-pollution monomers are selected from polyethylene glycol methacrylate, polyethylene glycol monoallyl ether, polyethylene glycol divinyl ether, polyethylene glycol dimethacrylate, methacryloyl ethyl sulfobetaine, 3- (methacrylamido) propyl-dimethyl- (3-sulfopropyl) ammonium, 4-vinyl-1- (3-sulfopropyl) pyridinium inner salt, acrylamide ethyl-N, N ' -dimethyl-N-propanesulfonate ammonium salt, methacryloyl oxyethyl-N, N ' -dimethyl-N-propanesulfonate ammonium salt, N ' -dimethyl-N- (2-methacryloyloxyethyl) -N- (3-propylsulfonic acid ammonium inner salt, One or more of N- (3-sulfopropyl) -N-methacrylamide propyl-N, N' -dimethyl betaine, methacryloyloxyethyl-N, N-diethyl propane sulfonate and carboxylic acid betaine methyl methacrylate, wherein the reactive monomer containing benzyl halide (Cl and Br) has a structural formula shown as follows:
wherein: x is selected from Cl or Br.
The membrane matrix material is selected from polyvinylidene fluoride, polyamide, polyvinyl chloride, polysulfone, polyether sulfone, polyacrylonitrile, polystyrene, polymethyl methacrylate, polyphenyl ether and polyether ether ketone.
The antibacterial component and the anti-pollution component are connected through a carbon-carbon bond.
The invention provides a preparation method of an antibacterial and anti-pollution microporous membrane, which comprises the following steps: (1) dissolving a membrane matrix material and the amphiphilic copolymer containing the tertiary amine in a solvent, uniformly mixing to prepare a membrane-making solution, and preparing an active precursor membrane containing the amphiphilic copolymer containing the tertiary amine by a non-solvent induced phase inversion method; (2) preparing a reactive monomer containing benzyl halide and a polymerization inhibitor into a solution, immersing the active precursor film prepared in the step (1) into the solution to perform quaternization reaction to generate a positively charged layer, and introducing a double-bond group on the surface of the positively charged layer; (3) preparing the anti-pollution monomer into a solution, immersing the membrane prepared in the step (2) into the solution, and initiating the copolymerization of the anti-pollution monomer on the surface of the membrane and the reactive monomer containing benzyl halide (Cl and Br) by adopting an initiator to generate an anti-pollution component to obtain the antibacterial anti-pollution microporous membrane, wherein the antibacterial component and the anti-pollution component are connected through a carbon-carbon bond.
The membrane matrix material in the step (1) is selected from polyvinylidene fluoride, polyamide, polyvinyl chloride, polysulfone, polyether sulfone, polyacrylonitrile, polystyrene, polymethyl methacrylate, polyphenyl ether and polyether ether ketone; the amphiphilic copolymer containing tertiary amine in the step (1) is obtained by copolymerizing a monomer containing tertiary amine and a hydrophobic monomer; the tertiary amine-containing monomer is selected from one or more of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, 4-vinylpyridine, 2-vinylpyridine and vinylimidazole; the hydrophobic monomer is selected from any one or more of methyl methacrylate, methyl acrylate, styrene, vinyl chloride, trifluoroethyl methacrylate, perfluorooctyl methacrylate, trifluoroethyl acrylate and perfluorooctyl acrylate; the solvent in the step (1) is selected from N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, acetone and dioxane.
Preferably, the proportion of the tertiary amine-containing monomer repeating units in the tertiary amine-containing amphiphilic copolymer is 10-90 wt%.
Preferably, the mass ratio of the amphiphilic copolymer containing tertiary amine to the film matrix material is 1/19-3/2.
In the invention, in order to further increase the hydrophilicity and permeability of the membrane matrix material, a hydrophilic additive can be added into the active precursor membrane containing the tertiary amine amphiphilic copolymer, wherein the hydrophilic additive is any one or more selected from polyethylene glycol, polyvinylpyrrolidone, polyether block copolymer, titanium dioxide, silicon dioxide, graphene, carbon nano-tubes, polydopamine nano-particles and lithium chloride. Such hydrophilic additives are essentially different from the anti-fouling components designed in the present invention. The hydrophilic additive only physically interacts with the membrane matrix, can keep hydrophilicity in the initial stage of use, but gradually loses along with the increase of the use time; the anti-contaminant component is attached to the matrix material with carbon-carbon bonds so that the anti-contaminant component is not lost with time.
The structural formula of the benzyl halide-containing monomer in the step (2) is as follows:
wherein X is selected from Cl or Br.
The solvent of the solution in the step (2) is selected from ethanol, n-heptane, cyclohexane, methanol, glycerol and n-hexane.
Preferably, the mass concentration of the benzyl halide-containing monomer in the solution is 0.5 to 10%.
The reaction temperature in the step (2) is 25-80 ℃, and the reaction time is 10 minutes-48 hours.
In the process of quaternization, a heating or reaction time prolonging mode is adopted to improve the quaternization degree, so that double bonds in the monomer containing the benzyl halide tend to be polymerized; therefore, the polymerization inhibitor is added in the quaternization process to prevent the self-polymerization of the monomer containing the benzyl halide during the heating or the reaction time prolonging.
The polymerization inhibitor in the step (2) is selected from any one or more of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone; the concentration range of the polymerization inhibitor is 0.1 to 1.0 weight percent of the concentration of the reactable monomer containing the benzyl halide.
The anti-pollution monomer in step (3) is selected from polyethylene glycol methacrylate, polyethylene glycol monoallyl ether, polyethylene glycol divinyl ether, polyethylene glycol dimethacrylate, methacryloyl ethyl sulfobetaine, 3- (methacrylamido) propyl-dimethyl- (3-sulfopropyl) ammonium, 4-vinyl-1- (3-sulfopropyl) pyridinium betaine, acrylamidoethyl-N, N ' -dimethyl-N-propanesulfonate ammonium salt, methacryloyloxyethyl-N, N ' -dimethyl-N-propanesulfonate ammonium salt, N ' -dimethyl-N- (2-methacryloyloxyethyl) -N- (3-propylsulfonic acid ammonium inner salt), N- (3-sulfopropyl) -N-methacrylamidopropyl-N, one or more of N' -dimethyl betaine, methacryloyloxyethyl-N, N-diethyl propanesulfonate and 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate.
The solvent of the solution containing the anti-pollution monomer in the step (3) is selected from water, water/ethanol, water/methanol and water/glycerol; preferably, the concentration of the anti-contaminant monomer in the solution is in the range of 0.5 wt% to 10 wt%.
The initiator in the step (3) is a water-soluble initiator selected from azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisdiisopropylimidazoline, potassium persulfate, ammonium persulfate, tert-butyl peroxide and ammonium persulfate/sodium bisulfite; preferably, the water-soluble initiator is added in an amount of 0.5 to 2 wt% based on the monomer concentration.
The polymerization temperature in the step (3) is 25-80 ℃, and the polymerization time is 10 minutes-2 hours.
The aperture range of the antibacterial and anti-pollution microporous membrane is 2 nanometers to 1 micron.
The antibacterial and anti-pollution microporous membrane can be applied to the fields of sewage treatment, tap water purification, food industry, seawater desalination pretreatment, biomedicine and the like.
Compared with the prior art, the invention has the following beneficial effects:
the antibacterial and anti-pollution microporous membrane provided by the invention simultaneously realizes the flux recovery rate of more than 95% and the bacteria killing rate of more than 99%, and simultaneously endows the microporous membrane with antibacterial property and anti-pollution functions. If the microporous membrane only has the anti-pollution performance, a small amount of or trace microorganisms still can be adsorbed on the surface of the microporous membrane, and the microorganisms on the adsorbed surface can gradually generate a biological membrane due to the reproduction and growth of the microorganisms, so that the anti-pollution performance of the microporous membrane is damaged; if the microporous membrane only has antibacterial performance, the microporous membrane has the capacity of killing microorganisms, but the microorganism corpses still have strong adsorption with the surface of the microporous membrane and gradually cover the surface so as to lose the antibacterial capacity of the surface.
The antibacterial component and the anti-pollution component in the antibacterial and anti-pollution microporous membrane provided by the invention are connected with the basement membrane through carbon-carbon bonds, and the antibacterial property and the anti-pollution function of the microporous membrane have long-term stability. Compared with the antibacterial and anti-pollution film based on silver ions, the antibacterial and anti-pollution film has no long-term stability because the silver ions gradually lose in the using process and simultaneously lose the antibacterial and anti-pollution functions.
According to the preparation method of the antibacterial and anti-pollution microporous membrane, provided by the invention, the adjustment of the antibacterial component and the anti-pollution component on the surface of the microporous membrane can be easily realized by adjusting the quaternization time and temperature and the conditions of the reaction time and temperature of the anti-pollution monomer and the reactive monomer containing benzyl halide.
The preparation method of the antibacterial and anti-pollution microporous membrane provided by the invention has the advantages that the composition of the base membrane is adjustable, the proportion of the antibacterial component to the anti-pollution component is adjustable, and the comprehensive performance adjustment of the microporous membrane, including membrane aperture, membrane permeability, membrane anti-pollution performance, membrane antibacterial performance and the like, can be easily realized.
Drawings
FIG. 1 shows the surface and cross-sectional morphology of an antibacterial and anti-fouling microporous membrane;
FIG. 2 is a schematic view of the surface chargeability of the antimicrobial anti-contamination microporous membrane;
FIG. 3 is a graph of an antimicrobial anti-fouling microporous membrane contamination test;
FIG. 4 is the comparison result of the antibacterial performance of the unmodified membrane and the antibacterial and anti-pollution microporous membrane.
Fig. 5 is a schematic structural view of an antibacterial and anti-pollution microporous membrane.
Detailed Description
The present invention will be described in detail with reference to examples.
As shown in fig. 5, the present invention relates to an antibacterial and anti-pollution microporous membrane, which comprises an antibacterial and anti-pollution separation layer and a support layer, wherein the antibacterial and anti-pollution separation layer comprises an antibacterial component and an anti-pollution component, the antibacterial component and the anti-pollution component are connected through a carbon-carbon bond, and the support layer comprises a membrane matrix material and an amphiphilic copolymer containing tertiary amine.
The antibacterial component is generated by carrying out quaternization reaction on a tertiary amine-containing amphiphilic copolymer and a reactable monomer containing benzyl halide (Cl and Br), wherein the tertiary amine-containing amphiphilic copolymer is obtained by copolymerizing a tertiary amine-containing monomer and a hydrophobic monomer; the anti-contaminant component is formed by copolymerizing an anti-contaminant monomer with a reactable monomer containing benzyl halides (Cl and Br).
The preparation method of the antibacterial and anti-pollution microporous membrane mainly comprises the following steps:
(1) dissolving a membrane matrix material and the amphiphilic copolymer containing the tertiary amine in a solvent, uniformly mixing to prepare a membrane-making solution, and preparing an active precursor membrane containing the amphiphilic copolymer containing the tertiary amine by a non-solvent induced phase inversion method;
(2) preparing a reactive monomer containing benzyl halide (Cl and Br) and a polymerization inhibitor into a solution, immersing the active precursor film prepared in the step (1) into the solution to carry out quaternization reaction to generate a positively charged layer, and introducing a double-bond group on the surface;
(3) preparing the anti-pollution monomer into a solution, immersing the membrane prepared in the step (2) into the solution, and initiating the copolymerization of the anti-pollution monomer on the surface of the membrane and the reactive monomer containing benzyl halide (Cl and Br) by adopting an initiator to generate an anti-pollution component to obtain the antibacterial anti-pollution microporous membrane, wherein the antibacterial component and the anti-pollution component are connected through a carbon-carbon bond.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and the detailed description. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
And (3) membrane structure characterization: observing the surface and the section morphology of the microporous membrane by a field emission scanning electron microscope; measuring the surface hydrophilicity and hydrophobicity of the microporous membrane by using a contact angle meter; measuring the charge property of the surface of the microporous membrane by Zeta potential; the pore size of the microporous membrane is determined by a PEG retention experiment or a pore meter.
And (3) membrane permeability characterization: the pure water flux was measured by a cross flow cell at a test pressure of 0.1MPa and a flow rate of 800 mL/min.
And (3) testing the anti-pollution performance: placing the microporous membrane sample in a cross flow cell device, taking 0.5g/L bovine serum albumin solution as a feed solution, and filtering for 30 min; 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 inverted, and the pure water flux was measured at 0.1MPa to calculate the flux recovery rate (pure water flux after back-flush/pure water flux × 100%).
And (3) testing antibacterial performance: culturing Staphylococcus aureus or Escherichia coli with TSB bacteria at 37 deg.C to a concentration of 108CFU/ml, diluted to 10 with PBS solution7CFU/ml; cutting a microporous membrane sample into a wafer with the diameter of 8mm by using a puncher, sterilizing the microporous membrane sample by using 75% alcohol, putting the microporous membrane sample into a porous plate, dropwise adding 10uL of bacterial liquid on the surface of the microporous membrane sample in a super clean bench, and culturing the porous plate in a constant-temperature oscillation box at 37 ℃ for 24 hours; the bacterial solution attached to the microporous membrane sample was washed with PBS and collected, diluted with PBS solution and plated to count, and the sterilization rate was calculated (sterilization rate ═ 1 — number of bacterial plaques on experimental sample/number of bacterial plaques on control sample × 100%).
Example 1:
6.75g of polyvinylidene fluoride powder, 2.25g of a methyl methacrylate film-dimethylaminoethyl methacrylate copolymer (wherein the content of dimethylaminoethyl methacrylate is 42%) and 2.5g of polyvinylpyrrolidone were dissolved in 41g N, N-dimethylacetamide, stirred uniformly at 60 ℃ and left to stand for deaeration. Pouring the membrane casting solution on a glass plate, uniformly scraping the membrane casting solution into a flat membrane with the thickness of about 250mm by using a scraper, and putting the flat membrane into deionized water at the temperature of 30 ℃ for phase conversion to form a membrane, thereby obtaining the active precursor membrane with the surface containing tertiary amine groups. The active precursor film was immersed in a solution of 20g of p-chloromethylstyrene (3 wt%) and hydroquinone (0.1% of monomer concentration) in isopropanol and reacted at 25 ℃ for 1 hour. The membrane was immersed in an aqueous solution of 100g of methacryloylethyl sulfobetaine (3 wt%), added with 0.03g of ammonium persulfate and 0.015g of sodium bisulfite, and reacted at 25 ℃ for 60min to obtain an antibacterial and anti-fouling microporous membrane.
Observing the surface and the section morphology of the microporous membrane by using a field emission scanning electron microscope (attached figure 1); measuring the surface hydrophilicity and hydrophobicity of the microporous membrane by using a contact angle meter (attached to table 2); measuring the charge property of the surface of the microporous membrane by adopting a Zeta potential (shown in figure 2); the pore diameter of the microporous membrane is determined by a PEG interception experiment (attached to the table 2); a cross flow cell is adopted to measure the pure water flux of the microporous membrane (attached to the table 2); the anti-pollution performance (figure 3) and the antibacterial performance (figure 4 and attached table 2) of the microporous membrane are measured. As can be seen from the figures and tables, the surface of the antibacterial and anti-pollution microporous membrane in example 1 is a dense layer, and the section of the antibacterial and anti-pollution microporous membrane is in a finger-shaped pore structure, so that the efficient separation performance and the high permeability of the microporous membrane can be realized; the active precursor film of the embodiment 1 is subjected to quaternization treatment, the surface of the microporous film is positively charged, and after the anti-pollution monomer is further introduced, the surface charge of the antibacterial anti-pollution microporous film is reduced; the antibacterial and anti-pollution microporous membrane of the embodiment 1 can realize the recovery of the flux of more than 95% through simple water washing after being polluted, which shows that the microporous membrane has excellent anti-pollution performance; the antibacterial and antipollution microporous membrane of the embodiment 1 has a sterilization rate of more than 99 percent on staphylococcus aureus and escherichia coli; 5nm of antibacterial and anti-pollution microporous membrane, and the pure water flux of 120L m-2h-1bar-1The hydrophilic contact angle was 55 °.
Comparative example 1: 6.75g of polyvinylidene fluoride powder, 2.25g of a methyl methacrylate film-dimethylaminoethyl methacrylate copolymer (wherein the content of dimethylaminoethyl methacrylate is 42%) and 2.5g of polyvinylpyrrolidone were dissolved in 41g N, N-dimethylacetamide, stirred uniformly at 60 ℃ and left to stand for deaeration. Pouring the membrane casting solution on a glass plate, uniformly scraping the membrane casting solution into a flat membrane with the thickness of about 250mm by using a scraper, and putting the flat membrane into deionized water at the temperature of 30 ℃ for phase conversion to form a membrane, thereby obtaining the active precursor membrane with the surface containing tertiary amine groups. The membrane was immersed in an aqueous solution of 100g of methacryloylethyl sulfobetaine (3 wt%), added with 0.03g of ammonium persulfate and 0.015g of sodium bisulfite, and reacted at 25 ℃ for 60min to obtain a modified microporous membrane I.
The characterization procedure was as in example 1. The result shows that the killing rate of the modified microporous membrane I to escherichia coli and staphylococcus aureus is less than 10 percent, the aperture of the modified microporous membrane II is 10nm, and the pure water flux is 240L m-2h-1bar-1The hydrophilic contact angle is 55 degrees, and the flux recovery rate can be more than 95 percent through simple water washing after pollution.
The surface chemical composition stability of the microporous membrane prepared in example 1 and the modified microporous membrane I was compared, and the stability of the performance was simulated by a method of soaking and washing in water for a long time. The results of the characterization by the total reflection surface infrared spectroscopy show that the surface chemical composition of the antibacterial and anti-pollution microporous membrane prepared in example 1 is completely consistent with the initial membrane composition after being soaked in water at 60 ℃ for 1 week, and the modified microporous membrane I obtained in comparative example 1 is soaked in water at 60 ℃ for 6 hours, and then the sulfonic acid group (-SO) on the infrared absorption peak is formed3-) the corresponding absorption peak disappears completely, which shows that the connection of carbon-carbon bonds is realized by taking the antibacterial layer as a transition layer between the substrate and the anti-pollution layer, and the stability of the antibacterial and anti-pollution layers is improved; in contrast, the stabilization of the chemical composition of the microporous membrane surface is not effectively provided by the surface in situ polymerization method alone.
Comparative example 2: 6.75g of polyvinylidene fluoride powder, 2.25g of a methyl methacrylate film-dimethylaminoethyl methacrylate copolymer (wherein the content of dimethylaminoethyl methacrylate is 42%) and 2.5g of polyvinylpyrrolidone were dissolved in 41g N, N-dimethylacetamide, stirred uniformly at 60 ℃ and left to stand for deaeration. Pouring the membrane casting solution on a glass plate, uniformly scraping the membrane casting solution into a flat membrane with the thickness of about 250mm by using a scraper, and putting the flat membrane into deionized water at the temperature of 30 ℃ for phase conversion to form a membrane, thereby obtaining the active precursor membrane with the surface containing tertiary amine groups. The active precursor film was immersed in a solution of 20g of p-chloromethylstyrene (3 wt%) and hydroquinone (0.1% of monomer concentration) in isopropanol and reacted at 25 ℃ for 1 hour to obtain a modified microporous film II.
The characterization method was the same as in example 2. The result shows that the killing rate of the modified microporous membrane II on escherichia coli and staphylococcus aureus is more than 99 percent, the aperture of the modified microporous membrane II is 10nm, and the pure water flux is 180L m-2h-1 bar-1The hydrophilic contact angle is 65 degrees, and the flux recovery rate can be only 55 percent through simple water washing after pollution, which shows that the sterilization performance is only introduced, and the service performance of the microporous membrane is seriously attenuated in the use process.
Example 2-example 16:
the preparation process of the antibacterial and anti-pollution microporous membrane is similar to that of example 1, wherein the reagents and reaction conditions are shown in attached table 1. The results of the characterization of the microporous membrane are shown in table 2. As can be seen from the table, the preparation method provided by the present invention can easily realize the adjustment of the antimicrobial component and the anti-pollution component on the surface of the microporous membrane by adjusting the quaternization time and temperature, and the reaction time and temperature conditions of the anti-pollution monomer and the reactable monomer containing the benzyl halide. In addition, the method of the invention enables the composition of the basement membrane to be adjustable, the proportion of the antibacterial component to the anti-pollution component to be adjustable, and the comprehensive performance adjustment of the microporous membrane, including membrane aperture, membrane permeability, membrane anti-pollution performance, membrane antibacterial performance and the like, can be easily realized. As can be seen from table 2, the antibacterial and anti-pollution microporous membrane prepared in the example can simultaneously achieve a flux recovery rate of 95% or more and a bacteria killing rate of 99% or more, and endow the microporous membrane with antibacterial and anti-pollution functions. Because the antibacterial component and the anti-pollution component in the membrane are connected with the basement membrane through carbon-carbon bonds, the antibacterial property and the anti-pollution function of the microporous membrane have long-term stability.
Attached table 2
Claims (10)
1. The antibacterial and anti-pollution microporous membrane is characterized by comprising an antibacterial and anti-pollution separation layer and a supporting layer, wherein the antibacterial and anti-pollution separation layer contains an antibacterial component and an anti-pollution component, the antibacterial component and the anti-pollution component are connected through a carbon-carbon bond, and the supporting layer is composed of a membrane matrix material and an amphiphilic copolymer containing tertiary amine.
2. The antimicrobial antipollution microporous membrane according to claim 1, wherein the antimicrobial component is formed by quaternization of a tertiary amine-containing amphiphilic copolymer and a reactable monomer containing benzyl halide, and the tertiary amine-containing amphiphilic copolymer is obtained by copolymerization of a tertiary amine-containing monomer and a hydrophobic monomer; the tertiary amine-containing monomer is selected from one or more of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, 4-vinylpyridine, 2-vinylpyridine and vinylimidazole; the hydrophobic monomer is selected from any one or more of methyl methacrylate, methyl acrylate, styrene, vinyl chloride, trifluoroethyl methacrylate, perfluorooctyl methacrylate, trifluoroethyl acrylate and perfluorooctyl acrylate; the reactive monomer containing the benzyl halide has the following structural formula:
wherein: x is selected from Cl or Br.
3. The antimicrobial soil resist microporous membrane according to claim 1, wherein the soil resist component is formed by copolymerizing a soil resist monomer selected from the group consisting of polyethylene glycol methacrylate, polyethylene glycol monoallyl ether, polyethylene glycol divinyl ether, polyethylene glycol dimethacrylate, methacryloyl ethyl sulfobetaine, 3- (methacrylamido) propyl-dimethyl- (3-sulfopropyl) ammonium, 4-vinyl-1- (3-sulfopropyl) pyridinium betaine, acrylamidoethyl-N, N ' -dimethyl-N-propanesulfonate ammonium salt, methacryloyloxyethyl-N, N ' -dimethyl-N-propanesulfonate ammonium salt, N ' -dimethyl-N- (2-methacryloyloxyethyl) -N- One or more of (3-propyl ammonium sulfonate inner salt), N- (3-sulfonic acid propyl) -N-methacrylamide propyl-N, N' -dimethyl betaine, methacryloxyethyl-N, N-diethyl propane sulfonate and carboxylic acid betaine methyl methacrylate, wherein the reactive monomer containing the benzyl halide has the following structural formula:
wherein: x is selected from Cl or Br.
4. The antimicrobial and anti-fouling microporous membrane of claim 1, wherein the membrane matrix material is selected from one of polyvinylidene fluoride, polyamide, polyvinyl chloride, polysulfone, polyethersulfone, polyacrylonitrile, polystyrene, polymethylmethacrylate, polyphenylene oxide, and polyetheretherketone.
5. A method for preparing an antibacterial anti-pollution microporous membrane according to claim 1, which comprises the following steps:
(1) dissolving a membrane matrix material and the amphiphilic copolymer containing the tertiary amine in a solvent, uniformly mixing to prepare a membrane-making solution, and preparing an active precursor membrane containing the amphiphilic copolymer containing the tertiary amine by a non-solvent induced phase inversion method;
(2) preparing a reactive monomer containing benzyl halide and a polymerization inhibitor into a solution, immersing the active precursor membrane prepared in the step (1) into the solution to carry out quaternization reaction to generate a positively charged layer, and introducing double-bond groups on the surface of the membrane;
(3) preparing the anti-pollution monomer into a solution, immersing the membrane prepared in the step (2) into the solution, and initiating the copolymerization of the anti-pollution monomer on the surface of the membrane and the reactive monomer containing the benzyl halide by adopting an initiator to generate an anti-pollution component to obtain the antibacterial anti-pollution microporous membrane, wherein the antibacterial component and the anti-pollution component are connected through a carbon-carbon bond.
6. The method for preparing an antibacterial and anti-pollution microporous membrane according to claim 5, wherein the solvent of the solution in the step (2) is selected from one or more of ethanol, n-heptane, cyclohexane, methanol, glycerol and n-hexane; the reaction temperature in the step (2) is 25-80 ℃, and the reaction time is 10 minutes-48 hours; the polymerization inhibitor in the step (2) is selected from any one or more of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone; the concentration range of the polymerization inhibitor is 0.1 to 1.0 weight percent of the concentration of the reactive monomer containing the benzyl halide.
7. The method of claim 5, wherein the solvent of the anti-microbial anti-fouling monomer-containing solution of step (3) is selected from the group consisting of water, water/ethanol, water/methanol, water/glycerol; the concentration range of the anti-pollution monomer is 0.5 to 10 weight percent; the adding amount of the water-soluble initiator is 0.5 to 2 weight percent of the monomer concentration.
8. The method of claim 5, wherein the initiator of step (3) is a water-soluble initiator selected from the group consisting of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisdiisopropylimidazoline, potassium persulfate, ammonium persulfate, t-butanol peroxide, ammonium persulfate/sodium bisulfite; the polymerization temperature in the step (3) is 25-80 ℃, and the polymerization time is 10 minutes-2 hours.
9. The anti-microbial, anti-fouling microporous membrane of claim 1 or prepared by the method of claim 5, wherein the anti-microbial, anti-fouling microporous membrane has a pore size ranging from 2 nm to 1 μm.
10. The use of the anti-microbial, anti-fouling microporous membrane of claim 1 or the anti-microbial, anti-fouling microporous membrane prepared by the method of claim 5 in sewage treatment, tap water purification, food industry, pre-desalination treatment of seawater, biomedical applications.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010970029.8A CN112237853B (en) | 2020-09-15 | 2020-09-15 | Antibacterial and anti-pollution microporous membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010970029.8A CN112237853B (en) | 2020-09-15 | 2020-09-15 | Antibacterial and anti-pollution microporous membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112237853A true CN112237853A (en) | 2021-01-19 |
| CN112237853B CN112237853B (en) | 2022-05-10 |
Family
ID=74170925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010970029.8A Active CN112237853B (en) | 2020-09-15 | 2020-09-15 | Antibacterial and anti-pollution microporous membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112237853B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114291922A (en) * | 2021-12-01 | 2022-04-08 | 江苏埃梯恩膜过滤技术有限公司 | Method and device for removing radionuclide in water |
| CN116212656A (en) * | 2023-04-23 | 2023-06-06 | 河北工业大学 | Preparation method of amphiphilic terpolymer ultrafiltration membrane |
| TWI808510B (en) * | 2021-10-15 | 2023-07-11 | 中原大學 | A zwitterionic material capable of preventing bio-inert performance decay, its fabricating membrane and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101011644A (en) * | 2006-12-27 | 2007-08-08 | 南京工业大学 | Method for persistent hydrophilic modification of polypropylene porous membrane surface |
| CN102218273A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院大连化学物理研究所 | Preparation method for hydrophilic ultrafiltration membrane |
| CN102688699A (en) * | 2012-05-23 | 2012-09-26 | 中国海洋大学 | Preparation method for antibacterial polyethersulfones ultrafilter membrane |
| CN105642129A (en) * | 2014-08-31 | 2016-06-08 | 浙江大学 | Positively charged nano-filtration membrane based on tertiary amine type amphiphilic copolymer and preparation method thereof |
-
2020
- 2020-09-15 CN CN202010970029.8A patent/CN112237853B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101011644A (en) * | 2006-12-27 | 2007-08-08 | 南京工业大学 | Method for persistent hydrophilic modification of polypropylene porous membrane surface |
| CN102218273A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院大连化学物理研究所 | Preparation method for hydrophilic ultrafiltration membrane |
| CN102688699A (en) * | 2012-05-23 | 2012-09-26 | 中国海洋大学 | Preparation method for antibacterial polyethersulfones ultrafilter membrane |
| CN105642129A (en) * | 2014-08-31 | 2016-06-08 | 浙江大学 | Positively charged nano-filtration membrane based on tertiary amine type amphiphilic copolymer and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI808510B (en) * | 2021-10-15 | 2023-07-11 | 中原大學 | A zwitterionic material capable of preventing bio-inert performance decay, its fabricating membrane and application |
| CN114291922A (en) * | 2021-12-01 | 2022-04-08 | 江苏埃梯恩膜过滤技术有限公司 | Method and device for removing radionuclide in water |
| CN116212656A (en) * | 2023-04-23 | 2023-06-06 | 河北工业大学 | Preparation method of amphiphilic terpolymer ultrafiltration membrane |
| CN116212656B (en) * | 2023-04-23 | 2024-05-10 | 河北工业大学 | Preparation method of amphiphilic terpolymer ultrafiltration membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112237853B (en) | 2022-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112237853B (en) | Antibacterial and anti-pollution microporous membrane and preparation method thereof | |
| Zhang et al. | Guanidinium-functionalized nanofiltration membranes integrating anti-fouling and antimicrobial effects | |
| You et al. | Preparation and characterization of antibacterial polyamine-based cyclophosphazene nanofiltration membranes | |
| Sui et al. | Antifouling and antibacterial improvement of surface-functionalized poly (vinylidene fluoride) membrane prepared via dihydroxyphenylalanine-initiated atom transfer radical graft polymerizations | |
| Zhu et al. | Effect of TiO2 content on the properties of polysulfone nanofiltration membranes modified with a layer of TiO2–graphene oxide | |
| CN112221354B (en) | Antibacterial and anti-pollution microporous membrane based on Michael addition reaction and preparation method thereof | |
| Wang et al. | Surface modification of NF membrane with zwitterionic polymer to improve anti-biofouling property | |
| Chiang et al. | A facile zwitterionization in the interfacial modification of low bio-fouling nanofiltration membranes | |
| Feng et al. | Highly effective antifouling performance of N-vinyl-2-pyrrolidone modified polypropylene non-woven fabric membranes by ATRP method | |
| Chen et al. | Antibacterial polyvinyl alcohol nanofiltration membrane incorporated with Cu (OH) 2 nanowires for dye/salt wastewater treatment | |
| Qin et al. | Surface modification of polyacrylonitrile membrane by chemical reaction and physical coating: Comparison between static and pore-flowing procedures | |
| Zhang et al. | A novel long-lasting antifouling membrane modified with bifunctional capsaicin-mimic moieties via in situ polymerization for efficient water purification | |
| JP2008520403A5 (en) | ||
| Kim et al. | Polysulfone based ultrafiltration membranes with dopamine and nisin moieties showing antifouling and antimicrobial properties | |
| Isawi | Development of thin-film composite membranes via radical grafting with methacrylic acid/ZnO doped TiO2 nanocomposites | |
| CN113908703B (en) | Charged nanofiltration membrane based on polymer nanoparticles and preparation method thereof | |
| CN113244780B (en) | Preparation method of anti-scaling and anti-yellowing composite reverse osmosis membrane | |
| JP6464866B2 (en) | Surface-modified substrate, polymer-coated substrate, and production method thereof | |
| Zhang et al. | Sulfaguanidine nanofiltration active layer towards anti-adhesive and antimicrobial attributes for desalination and dye removal | |
| Song et al. | Polyamide-poly (ionic liquid) reverse osmosis membrane with manifold excellent performance prepared via bionic capillary network for seawater desalinization | |
| Gao et al. | Composite NF membranes with anti-bacterial activity prepared by electrostatic self-assembly for dye recycle | |
| Zhao et al. | Improved permeability and biofouling resistance of microfiltration membranes via quaternary ammonium and zwitterion dual-functionalized diblock copolymers | |
| CN114917776A (en) | High-flux antibacterial reverse osmosis membrane and preparation method and application thereof | |
| Tian et al. | Preparation of reverse osmosis membrane with high permselectivity and anti-biofouling properties for desalination | |
| Ghasemi et al. | Enhancing fouling resistance and separation performance of polyethersulfone membrane through surface grafting with copolymerized thermo-responsive polymer and copper oxide nanoparticles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |