WO2023231312A1 - 纳滤膜的制备方法及由其制备的纳滤膜 - Google Patents

纳滤膜的制备方法及由其制备的纳滤膜 Download PDF

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WO2023231312A1
WO2023231312A1 PCT/CN2022/132633 CN2022132633W WO2023231312A1 WO 2023231312 A1 WO2023231312 A1 WO 2023231312A1 CN 2022132633 W CN2022132633 W CN 2022132633W WO 2023231312 A1 WO2023231312 A1 WO 2023231312A1
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group
preparation
solution
membrane
nanofiltration membrane
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PCT/CN2022/132633
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English (en)
French (fr)
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梁松苗
胡利杰
刘庚
宋鹏
张佳佳
王兵辉
文继斌
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沃顿科技股份有限公司
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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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • 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
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • 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
    • 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
    • B01D71/26—Polyalkenes
    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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

Definitions

  • the present disclosure relates to the technical field of water filtration membranes, and in particular to a preparation method of a nanofiltration membrane and a nanofiltration membrane prepared therefrom.
  • Membrane separation technology is a new and reliable separation technology with outstanding application performance in the fields of water treatment, pharmaceuticals, food, energy and chemical industry, attracting the attention of researchers.
  • nanofiltration membranes have been widely used in water treatment processes. Compared with reverse osmosis membranes, the successful application of nanofiltration membranes often stems from its selective separation of one solute.
  • One is the separation of salt ions of different valence states.
  • the second is In order to separate small organic molecules and salt ions, for example, in the textile industry, dye-containing wastewater often contains dyes and salt substances.
  • the nanofiltration process can intercept the dye and collect the salt substances for secondary use, and the dye is further Concentrated to a concentration that is easier to handle, therefore, nanofiltration membrane separation technology is currently the most cost-effective technology used to treat wastewater in the printing and dyeing industry.
  • the operating cost of the system is also crucial.
  • the operating pressure of the system can be effectively reduced and the operating cost of the nanofiltration membrane system can be significantly reduced.
  • the preparation of nanofiltration membranes with a loose-structured polyamide layer can effectively increase the permeation flux, which provides a better foundation for the practical application of nanofiltration membranes.
  • membrane fouling is the main obstacle to the application of membrane technologies such as nanofiltration membranes.
  • Membrane fouling refers to the adsorption and deposition that occurs on the surface of the membrane or in the membrane pores due to physical, chemical or mechanical interactions between suspended solids or soluble substances (microorganisms, macromolecules and colloidal salts, etc.) and the membrane during the filtration process of the membrane. , blockage and other phenomena.
  • the existence of membrane fouling will cause the flux of the membrane to attenuate and the life of the membrane to be reduced, which will increase the application cost of membrane separation technology. Alleviating membrane fouling has become a key technical problem in the application of membrane separation technology.
  • Membrane pollution is mainly divided into organic pollution, inorganic pollution, microbial pollution and colloidal pollution.
  • Organic pollution and inorganic pollution are reversible pollution, and microbial pollution and colloidal pollution are mainly irreversible pollution.
  • Microbial contamination on the membrane surface can be attributed to the biolayer formed by the adsorption and reproduction of bacteria, algae, etc. on the membrane surface.
  • antimicrobial treatment of the membrane surface is required to alleviate the permanent decline in membrane performance caused by irreversible microbial fouling.
  • the purpose of this disclosure is to provide a method for preparing a nanofiltration membrane and a nanofiltration membrane prepared thereby.
  • This nanofiltration membrane has both high throughput and selective separation (selective separation of organic dyes and inorganic salt ions) and excellent antibacterial properties during the water treatment process, and can effectively avoid microbial contamination.
  • the inventor of the present disclosure conducted intensive research and found that by introducing glycosidated sulfonamide substances as additives into the aqueous solution, the diffusion process of the aqueous monomer in the interfacial polymerization reaction can be changed, inducing looseness.
  • the formation of a structural polyamide functional layer can thereby increase the flux of the membrane.
  • the introduction of sulfonamide groups can bring antibacterial effects and reduce microbial contamination on the membrane surface; after the polyamide functional layer is formed through interfacial polymerization, The performance stability of nanofiltration membranes during long-term operation can be ensured by post-processing including hydroxylation and cross-linking.
  • the present disclosure provides a method for preparing a nanofiltration membrane, which is characterized by comprising the following steps:
  • the base film is contacted with the aqueous phase solution and the oil phase solution in sequence to perform an interfacial polymerization reaction on the base film to form a polyamide functional layer, wherein the aqueous phase solution contains aqueous phase monomers and additives, and the additives are Glycosylated sulfonamide compounds, the oil phase solution contains oil phase monomers;
  • a nanofiltration membrane is obtained through post-treatment, wherein the post-treatment includes hydroxylation treatment and cross-linking treatment.
  • polysulfone polysulfone
  • polyethersulfone sulfonated polyethersulfone
  • polyimide polyvinylidene fluoride
  • polyacrylonitrile polypropylene
  • polyvinyl chloride at least one of them.
  • the glycosidated sulfonamide compound is obtained by glycosylation reaction of a sugar compound and a compound containing a sulfonamide group, preferably, based on the total mass of the aqueous phase solution,
  • the mass percentage concentration of the glycosylated sulfonamide compound is 0.001 to 1.0 wt%.
  • the carbohydrate compound is selected from D-glucose, N-aryl glycoside, lactose, galactose, N-acetyl-D-glucosamine, arabinose, N-acetyl-D -At least one of galactosamine, D-ribose, L-rhamnose, xylose, mannose and maltose.
  • the compound containing a sulfonamide group is at least one selected from the compound represented by the following formula I and the compound represented by the following formula II:
  • R1 and R2 are at least one selected from the group consisting of H, hydrocarbon groups with 1 to 5 carbon atoms, amino groups and cyano groups, and R3, R4 and R5 are selected from the group consisting of H, amino groups, imino groups and hydroxyl groups. At least one of R3, R4 and R5 is amino;
  • R1 and R2 are hydrocarbon groups with 1 to 10 carbon atoms, and the hydrocarbon groups with 1 to 10 carbon atoms optionally contain amino, cyano, carboxyl, double bonds and ethynyl groups.
  • R3 is a hydrocarbon group with 1 to 5 carbon atoms
  • R4 is at least one selected from H and a hydrocarbon group with 1 to 10 carbon atoms
  • the hydrocarbon group with 1 to 10 carbon atoms is optional contains at least one selected from the group consisting of hydroxyl group, carboxyl group, ketone group, ether bond, carbonyl group, imino group, acyl group and phenyl group.
  • the water phase monomer is selected from the group consisting of piperazine, 2-methylpiperazine, polyethyleneimine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and homophenylenediamine.
  • At least one of benzenetriamines preferably, based on the total mass of the aqueous phase solution, the mass percentage concentration of the aqueous phase monomer is 0.1 to 3.0 wt%.
  • the oil phase monomer is selected from trimesoyl chloride, cyanuric chloride, dansyl chloride, isophthaloyl chloride, terephthaloyl chloride, phthaloyl chloride and At least one of diphenyl tetrayl chloride; preferably, based on the total mass of the oil phase solution, the mass percentage concentration of the oil phase monomer is 0.05 to 1.0 wt%.
  • the hydroxylation treatment is performed in a solution containing alcoholamine substances.
  • the alcoholamine substance is at least one selected from diethanolamine and triethanolamine, preferably Preferably, based on the total mass of the solution containing alcoholamine substances, the mass percentage concentration of the alcoholamine substances is 0.5 to 5.0 wt%.
  • the cross-linking treatment is performed in a solution containing a cross-linking agent.
  • the cross-linking agent is a dialdehyde compound with a carbon number of 2 to 6.
  • the cross-linking agent is Based on the total mass of the solution containing the cross-linking agent, the mass percentage concentration of the cross-linking agent is 0.01 to 0.5 wt%.
  • the present disclosure also provides a nanofiltration membrane prepared according to the preparation method of the present disclosure.
  • the nanofiltration membrane prepared by the preparation method of the present disclosure has a water flux as high as 80-120L/( m2 /h), and the removal rates of Congo red, methyl orange, and acid fuchsin can reach 99% and 82% respectively. ⁇ 90%, 90 ⁇ 95%, the removal rate of magnesium sulfate can be adjusted to 30%, thereby achieving selective separation of organic dye molecules and inorganic salt ions. In addition, it also has excellent antibacterial properties, effectively alleviating the Microbial contamination on the membrane surface during operation.
  • the preparation method provided by the present disclosure is simple and easy to operate.
  • the nanofiltration membrane can be applied to separation and concentration technologies in the fields of water treatment, dyes, biochemicals, food, environmental protection and other fields.
  • the present disclosure provides a method for preparing a nanofiltration membrane, which includes the following steps:
  • the base film is contacted with the aqueous phase solution and the oil phase solution in sequence to perform an interfacial polymerization reaction on the base film to form a polyamide functional layer, wherein the aqueous phase solution contains aqueous phase monomers and additives, and the additives are Glycosylated sulfonamide compounds, the oil phase solution contains oil phase monomers;
  • a nanofiltration membrane is obtained through post-treatment, wherein the post-treatment includes hydroxylation treatment and cross-linking treatment.
  • the technical concept of the present disclosure is that by introducing glycosylated sulfonamide substances as additives into the aqueous solution, the diffusion process of the aqueous monomer in the interfacial polymerization reaction can be changed, and the formation of a polyamide functional layer with a loose structure can be induced. Thereby increasing the flux of the membrane, and at the same time, the introduction of the sulfonamide group can bring antibacterial effect and reduce microbial contamination on the membrane surface; after the polyamide functional layer is formed through interfacial polymerization reaction, it is subjected to hydroxylation treatment and Post-processing, including cross-linking, can ensure the performance stability of nanofiltration membranes during long-term operation.
  • polymer is selected from polysulfone, polyethersulfone, sulfonated polyethersulfone, polyimide, polyvinylidene fluoride, polyacrylonitrile, polypropylene and polyvinyl chloride of at least one.
  • the mass percentage concentration of the polymer is 15 wt% to 25 wt%.
  • the solvent in the film casting liquid is N,N-dimethylformamide (DMF), N,N-dimethyl At least one of acetamide (DMAC), dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and imidazolinone.
  • DMF N,N-dimethylformamide
  • DMAC N,N-dimethyl At least one of acetamide (DMAC), dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and imidazolinone.
  • the film casting liquid optionally contains a non-solvent.
  • the non-solvent is alcohols with 1 to 6 carbon atoms, polyethylene glycol, polyvinylpyrrolidone, polypropylene glycol and polybutylene glycol. At least one.
  • alcohols having 1 to 6 carbon atoms include at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, hexanol, and the like. kind.
  • the non-solvent is preferably at least one of ethanol, n-propanol, isopropanol, n-butanol, polyethylene glycol, polypropylene glycol, polybutylene glycol, and polyvinylpyrrolidone.
  • the mass percentage concentration of the non-solvent is 0.5 to 5 wt%.
  • the reinforcing material used in the present disclosure may be polypropylene (PP) non-woven fabric, nylon (PA) non-woven fabric, ethylene (HDPE) non-woven fabric, polyester (PET) non-woven fabric.
  • PP polypropylene
  • PA nylon
  • HDPE ethylene
  • PET polyester
  • the method of coating the casting liquid on the non-woven fabric is not particularly limited. Coating methods commonly used in the field of nanofiltration membrane preparation can be used, such as casting, dip coating, blade coating, and spin coating. etc., and the blade coating method is more preferred. After coating on the non-woven fabric, it is then immersed in a coagulation bath to solidify the casting liquid into a film.
  • the pore diameter of the base film is not particularly limited, and is preferably 20 to 40 nm; the thickness of the base film is not particularly limited, and is preferably 35 to 45 ⁇ m.
  • the glycosidated sulfonamide compound is obtained by glycosylation reaction of a sugar compound and a compound containing a sulfonamide group.
  • Glycosylated sulfonamide compounds have both some properties of sugar substances and some properties of sulfonamide groups. They can change the diffusion process of polyamine monomers in the aqueous solution during the interfacial polymerization reaction and induce polymers with loose structures. The formation of the amide functional layer and the introduced sulfonamide group can bring antibacterial effects in subsequent applications.
  • the mass percentage concentration of the glycosidated sulfonamide compound is 0.001 to 1.0wt%, more preferably 0.05 to 0.5wt%; If the concentration of glycosidated sulfonamide compounds is lower than 0.001wt%, the flux of the membrane will not be significantly improved; if the concentration of glycosidated sulfonamide compounds is higher than 1.0wt%, the film-forming properties will be poor. Difference.
  • the carbohydrate compound has the property of being easily soluble in water, and is preferably selected from the group consisting of D-glucose, N-aryl glycosides, lactose, galactose, and N-acetyl-D-glucosamine. , at least one of arabinose, N-acetyl-D-galactosamine, D-ribose, L-rhamnose, xylose, mannose and maltose.
  • R1 and R2 are at least one selected from the group consisting of H, a hydrocarbon group having 1 to 5 carbon atoms, an amino group, and a cyano group.
  • the hydrocarbon group having 1 to 5 carbon atoms include methyl and ethyl. , isopropyl, etc.
  • R3, R4 and R5 are at least one selected from H, amino, imino and hydroxyl, and at least one of R3, R4 and R5 is amino.
  • Examples of the compound represented by formula I include p-aminobenzenesulfonamide, 3-aminobenzenesulfonamide, 5-amino-2-toluenesulfonamide, 4-aminomethylbenzenesulfonamide, and 2-aminophenol-4- Sulfonamide, 3,4-diaminobenzenesulfonamide, etc.
  • R1 and R2 are hydrocarbon groups with 1 to 10 carbon atoms, and the hydrocarbon groups with 1 to 10 carbon atoms optionally contain amino, cyano, carboxyl, double bonds and ethynyl groups.
  • R3 is a hydrocarbon group with 1 to 5 carbon atoms
  • R4 is at least one selected from H and a hydrocarbon group with 1 to 10 carbon atoms, wherein the hydrocarbon group with 1 to 10 carbon atoms is any
  • Optionally contains at least one selected from the group consisting of hydroxyl group, carboxyl group, ketone group, ether bond, carbonyl group, imino group, acyl group and phenyl group.
  • Examples of the compound represented by formula II include 2-aminoethylsulfonamide, 2-anilinoethanesulfonamide, 2-(2-phenylhydrazino)ethanesulfonamide, and 2-(2-benzoylhydrazide).
  • 2-aminoethylsulfonamide 2-anilinoethanesulfonamide
  • 2-(2-phenylhydrazino)ethanesulfonamide and 2-(2-benzoylhydrazide).
  • Ethanesulfonamide 2-(2-benzoylhydrazide)-N-ethynylethanesulfonamide
  • 2-(2-benzoylhydrazide)-N-ethynyl-N-propylethanesulfonamide 2-(2-benzoylhydrazide)-N-benzyl-N-ethynylethanesulfonamide, etc.
  • the water phase monomer is selected from the group consisting of piperazine, 2-methylpiperazine, polyethyleneimine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and phenylenediamine. At least one kind of triamine.
  • the mass percentage concentration of the aqueous phase monomer is 0.1 to 3.0 wt%, more preferably 0.5 to 1.5 wt%. If the content of the water phase monomer is less than 0.1wt%, it will lead to poor film formation and the prepared nanofiltration membrane will not have separation performance; if the content of the water phase monomer is higher than 3.0wt%, the prepared nanofiltration membrane will The polyamide functional layer of the membrane is thicker, which seriously increases the mass transfer resistance of water molecules, resulting in poor membrane performance.
  • a pH adjuster may optionally be included in the aqueous solution to adjust the pH value of the solution to a range of 9 to 12, thereby being more conducive to the interfacial polymerization reaction.
  • the pH adjuster may be at least one selected from the group consisting of sodium hydroxide, potassium hydrogen phosphate, potassium hydroxide, sodium carbonate, and triethylamine/camphorsulfonic acid. Among them, triethylamine and camphorsulfonic acid are used in combination to adjust the pH, which can make the reaction relatively mild. It is a common pH adjustment combination in interfacial polymerization reactions.
  • the contact time and temperature of the base film and the aqueous solution are not particularly limited, but the contact time is preferably in the temperature range of 15 to 45° C. for 10 to 60 seconds.
  • oil phase monomer is selected from the group consisting of trimesoyl chloride, cyanuric acid chloride, dansyl chloride, isophthaloyl chloride, terephthaloyl chloride, phthaloyl chloride and dihydrochloride. At least one kind of pyromellitic acid chloride.
  • the mass percentage concentration of the oil phase monomer is 0.05 to 1.0 wt%, more preferably 0.1 to 0.5 wt%. If the content of the oil phase monomer is less than 0.05wt%, the polyamide functional layer cannot be formed to meet the performance requirements of the nanofiltration membrane; if the content of the oil phase monomer is higher than 1.0wt%, the flux of the prepared nanofiltration membrane The drop is severe and there is even no flux.
  • the solvent in the oil phase solution is not particularly limited, and examples include n-hexane, n-heptane, cyclohexane, ethylcyclohexane, Isopar M, Isopar H, Isopar L, Isopar E, Isopar G, etc.
  • the contact time and temperature of the base film and the oil phase solution are not particularly limited, but the contact is preferably in the temperature range of 15 to 45° C. for 10 to 60 seconds.
  • heating can be performed to further cross-link the polyamide functional layer.
  • the heating temperature is 25 Within the range of ⁇ 40°C, the heating time is 1 to 5 minutes.
  • the purpose of heating is to further promote the volatilization of the solvent and the cross-linking and curing of the polyamide functional layer. If the heating temperature is too high or the heating time is too long, the microstructure on the membrane surface will be torn, resulting in a reduction in the desalination performance of the membrane.
  • the post-treatment includes hydroxylation treatment and cross-linking treatment
  • the hydroxylation treatment refers to hydroxylating the oil phase monomers in the oil phase solution that have not undergone interfacial polymerization
  • the hydroxylation treatment is carried out in a solution containing alcoholamine substances.
  • the alcoholamine substance is at least one selected from diethanolamine and triethanolamine, and its function is to induce acid chlorides that do not participate in the interfacial polymerization reaction.
  • the monomer-like acid chloride group is hydroxylated to introduce hydroxyl groups on the surface of the membrane.
  • alcoholamines are covalently bonded to unreacted acid chloride groups, causing the amino groups in the alcoholamines to react, leaving hydroxyl groups on the membrane surface, thus enhancing the hydrophilicity of the membrane surface and making the membrane more durable in the long term.
  • the pollution during operation is alleviated and the degradation of membrane performance caused by pollution is reduced.
  • the glycosidated sulfonamide compounds in the aqueous phase solution is lower than that of the aqueous phase monomer, the glycosidated sulfonamide compounds are not combined with the polyamide functional layer through chemical bonds and will not be used during the long-term operation of the membrane. , the glycosylated sulfonamide compounds will fall off, resulting in the impairment of the antibacterial stability of the membrane.
  • the glycosylated sulfonamide compounds present in the membrane are combined with the hydroxyl groups on the membrane surface under the action of the cross-linking agent, and are fixed in the polyamide functional layer through chemical bonding to ensure Improve the antibacterial stability of the membrane during use.
  • the mass percentage concentration of the alcoholamine substances is 0.5 to 5.0 wt%.
  • the oil that has not undergone interfacial polymerization can be The phase monomers (acyl chloride monomers) are not all hydroxylated, and the unhydroxylated acid chloride monomers are hydrolyzed to produce carboxyl groups, which makes the membrane surface negatively charged, causing repulsion with negatively charged dyes and inorganic salts, thereby promoting Retains dyes and inorganic salts.
  • the mass percentage concentration of alcoholamine substances is 1.0 to 3.0 wt%.
  • the solution is immersed in a solution containing alcoholamine substances in a temperature range of 40 to 60° C. for 0.5 to 5 minutes.
  • the solution containing alcoholamine substances may also optionally contain a pH adjuster to adjust the pH value of the solution to a range of 9 to 11, thereby being more conducive to the reaction.
  • the pH adjuster may be at least one selected from the group consisting of sodium hydroxide, potassium hydrogen phosphate, potassium hydroxide, sodium carbonate, and triethylamine/camphorsulfonic acid.
  • the cross-linking treatment is carried out in a solution containing a cross-linking agent.
  • the above-mentioned hydroxylation modification is left on the surface of the film.
  • the hydroxyl group is further cross-linked and fixed with the hydroxyl group and amino group of the glycosylated sulfonamide compound, so that the glycosylated sulfonamide compound stably exists in the polyamide functional layer to ensure the stable performance of the membrane during long-term operation.
  • the cross-linking agent is a dialdehyde compound having 2 to 6 carbon atoms.
  • dialdehyde compound having 2 to 6 carbon atoms. Examples include glyoxal, malondialdehyde, succinic aldehyde, glutaraldehyde, and the like.
  • the mass percentage concentration of the cross-linking agent is 0.01 to 0.5 wt%, more preferably 0.02 to 0.1 wt%.
  • the immersion time in the solution containing the cross-linking agent is 1 to 5 minutes, more preferably 2 to 4 minutes. This process is mainly to further enhance and ensure the performance of the nanofiltration membrane. If the concentration of the cross-linking agent is too low or the immersion time is insufficient, the effect will not meet the expectations. If the concentration of the cross-linking agent is too high or the immersion time is too long, the effect will not be as expected. It will also lead to a reduction in the overall performance of the membrane.
  • the post-treatment of the preparation method described in the present disclosure can also include two stages of water washing.
  • the first stage of water washing temperature is 40-60°C
  • the second stage of water washing temperature is 20-30°C to wash away unreacted amines. Residuals from the aforementioned processes such as monomers, acid chloride monomers, glycosylated sulfonamide compounds, cross-linking agents, etc.
  • the surface of the nanofiltration membrane is then coated with a protective layer solution
  • the protective layer solution contains a polyhydroxy polymer, such as polyvinyl alcohol, polyethylene glycol, and the like.
  • the function of the protective layer solution is to reduce damage to the surface of the nanofiltration membrane during the subsequent heating and drying process and ensure the stability of the membrane structure.
  • the content of the polyhydroxy polymer is 1 to 3 wt%, more preferably 1.5 to 2.5 wt%, and further preferably, the coating time is 5 to 20 seconds.
  • the protective layer solution may optionally contain at least one selected from hydrochloric acid and glutaraldehyde, where the main purpose of adding hydrochloric acid is to adjust the pH value of the solution and promote the production of polyhydroxy polymers such as polyvinyl alcohol,
  • the dissolution of polyethylene glycol, etc., and the addition of a small amount of glutaraldehyde can promote the self-crosslinking of the polyhydroxy polymers such as polyvinyl alcohol, polyethylene glycol, etc., and can better form a protective layer during coating.
  • heating and drying post-processing is performed to obtain the final nanofiltration membrane.
  • the heating and drying temperature range is 50-90°C, and the drying time is 1-3 minutes.
  • non-limiting examples are as follows:
  • DMF dimethylformamide
  • DMAC dimethylacetamide
  • the present disclosure also provides nanofiltration membranes prepared according to the preparation methods of the present disclosure.
  • the nanofiltration membrane prepared by the preparation method of the present disclosure has a water flux as high as 80-120L/( m2 /h), and the removal rates of Congo red, methyl orange, and acid fuchsin can reach 99% and 82% respectively. ⁇ 90%, 90 ⁇ 95%, the removal rate of magnesium sulfate can be adjusted to 30%, thereby achieving selective separation of organic dye molecules and inorganic salt ions. In addition, it also has excellent antibacterial properties, effectively alleviating the Microbial contamination on the membrane surface during operation.
  • the nanofiltration membrane can be applied to separation and concentration technologies in the fields of water treatment, dyes, biochemicals, food, environmental protection and other fields.
  • disodium hydrogen phosphate weigh 28.4g disodium hydrogen phosphate and dissolve it in 100ml water, add water to dilute to 1000ml and set aside; weigh 24g sodium dihydrogen phosphate and dissolve it in 100ml water and add water to dilute it to 1000ml and set aside; weigh 68.5ml sodium dihydrogenphosphate aqueous solution and 31.5ml Place the aqueous solution of disodium hydrogen phosphate in a beaker, mix evenly to prepare a phosphate buffer solution with a pH value of 6.5, and set aside.
  • the base film was prepared by the immersion precipitation method.
  • the film casting solution contained 18wt% polysulfone and 2wt% polyethylene glycol 400, in which the solvent was N,N-dimethylformamide, and was stirred at a temperature of 60°C for 6 hours. Then put it into a constant temperature deaeration of 25°C for 12 hours; scrape the degassed casting liquid on polyester PET non-woven fabric with a film scraper.
  • the thickness of the base film is 40 ⁇ m, and it is immersed in pure water with a temperature of 15°C.
  • the film is solidified in a cold water bath and washed with water to obtain a polysulfone support layer base film with a porous structure.
  • a diethanolamine solution is prepared according to the following conditions: diethanolamine is 3wt%, triethylamine is 2wt%, camphorsulfonic acid is 4wt%, and the balance is pure water.
  • Comparative Example 2 was conducted in the same manner as Comparative Example 1, except that after obtaining the primary nanofiltration membrane, it was immersed in a 50° C. diethanolamine solution for 2 minutes and then immersed in a cross-linking agent solution at room temperature for 2 minutes.
  • Example 1 was performed in the same manner as Comparative Example 2, except that 1 g or more of the synthesized glycosidated sulfonamide compound 1-1 was added to the aqueous solution.
  • Comparative Example 3 was conducted in the same manner as Comparative Example 1, except that 1 g or more of the synthesized glycosidated sulfonamide compound 1-1 was added to the aqueous phase solution.
  • Example 2 In addition to replacing the glycosylated sulfonamide compound 1-1 with the above-synthesized glycosylated sulfonamide compounds 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, and 2-1 respectively. , 2-2, 2-3, 3-1, 3-2, and 3-3, Examples 2 to 13 were carried out in the same manner as Example 1.
  • the nanofiltration membranes obtained in Comparative Examples 1 to 3 and Examples 1 to 13 were tested on a cross-flow membrane test bench respectively.
  • the test conditions were 0.1g/L dye + 1g/L magnesium sulfate aqueous solution (wherein The dyes are Congo red, methyl orange and acid fuchsin.
  • the test a mixed solution of the three dyes and magnesium sulfate was tested respectively), operating pressure of 70psi, temperature of 25°C, and pH value of 7.
  • the test stability time is 40 minutes.
  • Comparative Example 3 In addition, during the test, it was observed that in Comparative Example 3, there was a gradual decrease in the selective separation performance during the test stability time, while in Examples 1 to 13, no obvious decrease in the selective separation performance was observed. Comparing Comparative Example 3 with Examples 1 to 13, it can be seen that for the nanofiltration membrane to which glycosylated sulfonamide compounds are added, the additive glycosylated sulfonamides can be effectively fixed by performing hydroxylation treatment and cross-linking treatment. compound to ensure that the membrane does not suffer from large defects that would lead to a reduction in separation performance.
  • Preparation of culture medium Dissolve 5.0g beef extract, 10.0g peptone and 5.0g NaCl in 1L pure water, stir evenly, and adjust the pH value to neutral. Then, it was sterilized in an autoclave at a temperature of 120° C. for 20 minutes to obtain a liquid culture medium. Add 18g agar to the liquid culture medium and sterilize it to obtain a solid culture medium.
  • the bacteria were cultured in a liquid medium at 37°C for 24 hours.
  • the culture medium containing bacteria was continuously shaken, centrifuged to obtain bacterial cells, and diluted with PBS.
  • a membrane sample with an area of 3cm ⁇ 3cm was immersed in 15mL of bacterial suspension and taken out after 15 hours.
  • the bacterial suspension diluted to 0.1 mL was evenly coated on the solid medium and then incubated at 37°C for 24 hours. Finally, count the number of colonies on the solid medium. All operations are performed in a sterile environment. The number of growing bacteria is calculated according to the following formula:
  • ABA antibacterial activity
  • Np is the number of colonies growing on the polysulfone base membrane
  • Ns is the number of colonies growing on the nanofiltration membrane
  • the present disclosure provides a method for preparing a nanofiltration membrane, which is simple and easy to operate.
  • the nanofiltration membrane prepared by the preparation method of the present disclosure has a water flux as high as 80-120L/( m2 /h), and the removal rates of Congo red, methyl orange, and acid fuchsin can reach 99% and 82% respectively. ⁇ 90%, 90 ⁇ 95%, and the removal rate of magnesium sulfate can be adjusted to 30%, thereby achieving selective separation of organic dye molecules and inorganic salts. In addition, it also has excellent antibacterial properties, effectively easing the problem during operation. Microbial contamination on the membrane surface during the process.
  • the nanofiltration membrane provided by the present disclosure can be used for effective selective separation in fields such as water treatment, dyes, biochemicals, food, and environmental protection.

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Abstract

本公开涉及纳滤膜的制备方法及由其制备的纳滤膜。所述制备方法包括以下步骤：制备铸膜液，使铸膜液在增强材料上固化形成基膜；将所述基膜依次与水相溶液和油相溶液接触以在所述基膜上进行界面聚合反应形成聚酰胺功能层，其中所述水相溶液包含水相单体和添加剂，所述添加剂为糖苷化磺酰胺类化合物，所述油相溶液包含油相单体；经后处理得到纳滤膜，所述后处理包括羟基化处理和交联处理。通过本公开的制备方法制备的纳滤膜具备高通量和选择性分离性能以及优异的抗菌性能，能够有效地避免微生物污染。

Description

纳滤膜的制备方法及由其制备的纳滤膜 技术领域
本公开涉及水过滤膜的技术领域，尤其涉及纳滤膜的制备方法和由其制备的纳滤膜。
背景技术
随着经济的发展，人们对印染和纺织的需求逐渐增加。近年来，染料的生产和使用量大幅度增加，在这个过程中，会产生大量的含染料的废水，如果将这些未经处理的含染料的废水直接排放，会导致严重的环境污染问题。因此，含染料的废水的处理以及回收再利用成为当前急需解决的环境问题之一。除此之外，在染料的使用过程中，会加入大量无机盐以提高生产和染色效率，这加剧了染料回收的难度。如何实现含染料的废水中活性染料与无机盐的有效分离，达到回收和重复利用，是当前研究的一个重点。
膜分离技术是一种新型可靠的分离技术，在水处理、制药、食品、能源及化工等领域有着杰出的应用表现，吸引了广大研究人员的注意。其中，纳滤膜已被广泛用于水处理过程。与反渗透膜相比，纳滤膜的成功应用往往源于它对一种溶质的选择性分离。其一为对不同价态的盐离子的分离，如在地下水的软化过程中，通过纳滤过程，能够有效地去除水中的钙镁离子而保留钠离子，从而有效地降低水的硬度；其二为对有机小分子和盐离子的分离，如在纺织行业中，含染料的废水往往含有染料和盐类物质，通过纳滤过程可以截留染料而收集盐类物质进行二次利用，而染料也进一步浓缩到更容易处理的浓度，因此，纳滤膜分离技术是目前用于处理印染行业废水的最经济有效的技术。
在纳滤膜系统的实际应用过程中，除了考虑纳滤膜的截留性能以外，系统的运行成本也是至关重要的。通过提高纳滤膜的水通量，可以有效地降低系统的运行压力，大幅度的降低纳滤膜系统的运行成本。在纳滤膜类别中，制备具有疏松结构的聚酰胺层的纳滤膜可以有效地提高渗透通量，这为纳滤膜的实际应用带来了较好的基础。
目前已经有很多研究集中于如何制备具有疏松结构的聚酰胺层的纳滤膜，如在专利文献CN111450715B中提及在基膜制备中加入无机盐，采用单宁酸为水相溶液，制备出具有疏松结构的纳滤膜。在专利文献CN112058094B中，研究人员将聚脲微球加入到基膜中， 对基膜表面进行交联处理制备出具有疏松结构的纳滤膜。
需要注意的是，膜的污染是纳滤膜等膜技术应用的主要障碍。膜的污染是指在膜的过滤过程中，悬浮物或可溶性物质(微生物、大分子和胶体盐等)与膜发生物理化学作用或机械作用而在膜的表面或膜孔内发生的吸附、沉积、堵塞等现象。膜的污染的存在，会导致膜的通量衰减，膜的寿命减少，这会造成膜分离技术的应用成本增加。缓解膜的污染已经成为膜分离技术应用的关键技术难题。
膜的污染主要分为有机污染、无机污染、微生物污染和胶体污染，其中有机污染和无机污染为可逆污染，微生物污染和胶体污染主要为不可逆污染。膜表面的微生物污染可以归结为细菌、藻类等在膜表面的吸附、繁殖形成的生物层。为了避免在膜表面形成污染，需要对膜表面进行抗菌处理，以达到缓解由于不可逆的微生物污染导致的膜性能的永久性下降。
因此，如何制备具有较好的渗透和分离性能且兼具抗微生物污染的纳滤膜，是当前纳滤膜研究中的一大技术热点。
发明内容
发明要解决的问题
针对现有技术中存在的技术问题，本公开的目的在于提供一种纳滤膜的制备方法及由其制备的纳滤膜。该纳滤膜在水处理过程中同时具备高通量和选择性分离(有机染料和无机盐离子的选择性分离)性能以及优异的抗菌性能，能够有效地避免微生物污染。
用于解决问题的方案
本公开的发明人为了实现以上目的，进行锐意研究之后发现：通过在水相溶液中引入糖苷化磺酰胺类物质作为添加剂，可以改变水相单体在界面聚合反应中的扩散过程，诱导具有疏松结构的聚酰胺功能层的形成，从而提高膜的通量，同时磺酰胺基团的引入能够带来抗菌效果，降低在膜表面上的微生物污染；在通过界面聚合反应形成聚酰胺功能层之后，通过对其进行包括羟基化处理和交联处理在内的后处理能够确保纳滤膜在长期运行过程中的性能稳定性。
本公开提供一种纳滤膜的制备方法，其特征在于，包括以下步骤：
制备铸膜液，使所述铸膜液在增强材料上固化形成基膜，其中所述铸膜液包含聚合物和溶剂；
将所述基膜依次与水相溶液和油相溶液接触以在所述基膜上进行界面聚合反应形成聚酰胺功能层，其中所述水相溶液包含水相单体和添加剂，所述添加剂为糖苷化磺酰胺类化合物，所述油相溶液包含油相单体；
经后处理得到纳滤膜，其中所述后处理包括羟基化处理和交联处理。
根据本公开所述的制备方法，其中所述聚合物为选自聚砜、聚醚砜、磺化聚醚砜、聚酰亚胺、聚偏氟乙烯、聚丙烯腈、聚丙烯和聚氯乙烯中的至少一种。
根据本公开所述的制备方法，其中所述糖苷化磺酰胺类化合物通过将糖类化合物与含磺酰胺基团的化合物进行糖苷化反应得到，优选地，基于所述水相溶液的总质量，所述糖苷化磺酰胺类化合物的质量百分比浓度为0.001～1.0wt％。
根据本公开所述的制备方法，其中所述糖类化合物为选自D-葡萄糖、N-芳基糖苷、乳糖、半乳糖、N-乙酰-D-氨基葡萄糖、阿拉伯糖、N-乙酰-D-半乳糖胺、D-核糖、L-鼠李糖、木糖、甘露糖和麦芽糖中的至少一种。
根据本公开所述的制备方法，其中所述含磺酰胺基团的化合物为选自由下式I表示的化合物和下式II表示的化合物中的至少一种：
Figure PCTCN2022132633-appb-000001
在式I中，R1和R2为选自H、碳原子数为1至5的烃基、氨基和氰基中的至少一种，R3、R4和R5为选自H、氨基、亚氨基和羟基中的至少一种，R3、R4和R5中至少之一为氨基；
Figure PCTCN2022132633-appb-000002
在式II中，R1和R2为碳原子数为1至10的烃基，所述碳原子数为1至10的烃基任选地含有选自氨基、氰基、羧基、双键和乙炔基中的至少一种，R3为碳原子数为1至5的烃基，R4为选自H、碳原子数为1至10的烃基中的至少一种，所述碳原子数为1至10的烃基任选地含有选自羟基、羧基、酮基、醚键、羰基、亚氨基、酰基和苯基中的至少一种。
根据本公开所述的制备方法，其中所述水相单体为选自哌嗪、2-甲基哌嗪、聚乙烯亚胺、间苯二胺、对苯二胺、邻苯二胺和均苯三胺中的至少一种；优选地，以所述水相溶液的总质量计，所述水相单体的质量百分比浓度为0.1～3.0wt％。
根据本公开所述的制备方法，其中所述油相单体为选自均苯三甲酰氯、氰脲酰氯、丹磺酰氯、间苯二甲酰氯、对苯二甲酰氯、邻苯二甲酰氯和联苯四酰氯中的至少一种；优选地，以所述油相溶液的总质量计，所述油相单体的质量百分比浓度为0.05～1.0wt％。
根据本公开所述的制备方法，其中所述羟基化处理在包含醇胺类物质的溶液中进行，优选地，所述醇胺类物质为选自二乙醇胺、三乙醇胺中的至少一种，优选地，以所述包含醇胺类物质的溶液的总质量计，醇胺类物质的质量百分比浓度为0.5～5.0wt％。
根据本公开所述的制备方法，其中所述交联处理在包含交联剂的溶液中进行，所述交联剂为碳原子数为2至6的二醛类化合物，优选地，以所述包含交联剂的溶液的总质量计，交联剂的质量百分比浓度为0.01～0.5wt％。
本公开还提供一种根据本公开所述的制备方法制得的纳滤膜。
发明的效果
采用本公开的制备方法制备的纳滤膜具有高达80～120L/(m 2/h)的水通量，对于刚果红、甲基橙、酸性品红的脱除率分别可以达到99％、82～90％、90～95％，对于硫酸镁的脱除率可以调节至30％，从而实现对于有机染料分子和无机盐离子的选择性分离，此外还具有优异的抗菌性能，有效地缓解了在运行过程中在膜的表面上的微生物污染。本公开提供的制备方法简单、易于操作。所述纳滤膜可以应用于水处理、染料、生物化工、食品、环保等领域的分离和浓缩技术。
具体实施方式
本公开提供一种纳滤膜的制备方法，其包括以下步骤：
制备铸膜液，使所述铸膜液在增强材料上固化形成基膜，其中所述铸膜液包含聚合物和溶剂；
将所述基膜依次与水相溶液和油相溶液接触以在所述基膜上进行界面聚合反应形成聚酰胺功能层，其中所述水相溶液包含水相单体和添加剂，所述添加剂为糖苷化磺酰胺类化合物，所述油相溶液包含油相单体；
经后处理得到纳滤膜，其中所述后处理包括羟基化处理和交联处理。
本公开的技术构思在于：通过在水相溶液中引入糖苷化磺酰胺类物质作为添加剂，可以改变水相单体在界面聚合反应中的扩散过程，诱导具有疏松结构的聚酰胺功能层的形成，从而提高膜的通量，同时磺酰胺基团的引入能够带来抗菌效果，降低在膜表面上的微生物污染；在通过界面聚合反应形成聚酰胺功能层之后，通过对其进行包括羟基化处理和交联处理在内的后处理能够确保纳滤膜在长期运行过程中的性能稳定性。
本公开所述的制备方法，其中所述聚合物为选自聚砜、聚醚砜、磺化聚醚砜、聚酰亚胺、聚偏氟乙烯、聚丙烯腈、聚丙烯和聚氯乙烯中的至少一种。
优选地，基于所述铸膜液的总质量，所述聚合物的质量百分比浓度为15wt％～25wt％。
对于所述铸膜液中的溶剂没有特别限制，只要其能够充分溶解聚合物即可，优选地，所述溶剂为N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、二甲基亚砜、N-甲基吡咯烷酮、四氢呋喃和咪唑啉酮中的至少一种。
在所述铸膜液中任选地含有非溶剂，优选地，所述非溶剂为碳数为1～6的醇类、聚乙二醇、聚乙烯吡咯烷酮、聚丙二醇和聚丁二醇中的至少一种。作为碳数为1～6的醇类可以列举甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、正戊醇、异戊醇和己醇等中的至少一种。所述非溶剂优选为乙醇、正丙醇、异丙醇、正丁醇、聚乙二醇、聚丙二醇、聚丁二醇、聚乙烯吡咯烷酮中的至少一种。优选地，基于所述铸膜液的总质量，所述非溶剂的质量百分比浓度为0.5～5wt％。
在本公开中使用的增强材料可以为聚丙烯(PP)无纺布、锦纶(PA)无纺布、乙纶(HDPE)无纺布、聚酯(PET)无纺布。
对于将铸膜液涂覆在无纺布上的方法没有特别限定，可以使用纳滤膜制备领域中通常使用的涂覆方法，例如流延法、浸涂法、刮涂法、旋转涂覆法等，更优选为刮涂法。 涂覆在无纺布上之后接着浸在凝固浴中，使得铸膜液凝固成膜。
对于基膜的孔径没有特别限制，优选为20～40nm；对于基膜的厚度没有特别限制，优选为35～45μm。
本公开所述的制备方法，其中所述糖苷化磺酰胺类化合物通过将糖类化合物与含磺酰胺基团的化合物进行糖苷化反应得到。糖苷化磺酰胺类化合物同时具有糖类物质的部分性质和磺酰胺基团的部分性质，可以改变水相溶液中的多元胺类单体在界面聚合反应中的扩散过程，诱导具有疏松结构的聚酰胺功能层的形成，同时，引入的磺酰胺基团能够在后续应用过程中带来抗菌效果。
本公开所述的制备方法，优选地，基于所述水相溶液的总质量，所述糖苷化磺酰胺类化合物的质量百分比浓度为0.001～1.0wt％，更优选地为0.05～0.5wt％；如果糖苷化磺酰胺类化合物的浓度含量低于0.001wt％，则会导致膜的通量提升不明显；如果糖苷化磺酰胺类化合物的浓度含量高于1.0wt％，则会导致成膜性较差。
本公开所述的制备方法，其中所述糖类化合物具有易溶于水的性质，优选地为选自D-葡萄糖、N-芳基糖苷、乳糖、半乳糖、N-乙酰-D-氨基葡萄糖、阿拉伯糖、N-乙酰-D-半乳糖胺、D-核糖、L-鼠李糖、木糖、甘露糖和麦芽糖中的至少一种。
本公开所述的制备方法，其中所述含磺酰胺基团的化合物为选自由下式I表示的化合物和下式II表示的化合物中的至少一种：
Figure PCTCN2022132633-appb-000003
在式I中，R1和R2为选自H、碳原子数为1至5的烃基、氨基和氰基中的至少一种，作为碳原子数为1至5的烃基可以列举甲基、乙基、异丙基等，R3、R4和R5为选自H、氨基、亚氨基和羟基中的至少一种，R3、R4和R5中至少之一为氨基。
作为由式I表示的化合物，可以列举如对氨基苯磺酰胺、3-氨基苯磺酰胺、5-氨基-2-甲苯磺酰胺、4-氨基甲基苯磺酰胺、2-氨基苯酚-4-磺酰胺、3,4-二氨基苯磺酰胺等。
Figure PCTCN2022132633-appb-000004
在式II中，R1和R2为碳原子数为1至10的烃基，所述碳原子数为1至10的烃基任选地含有选自氨基、氰基、羧基、双键和乙炔基中的至少一种，R3为碳原子数为1至5的烃基，R4为选自H、碳原子数为1至10的烃基中的至少一种，其中所述碳原子数为1至10的烃基任选地含有选自羟基、羧基、酮基、醚键、羰基、亚氨基、酰基和苯基中的至少一种。
作为由式II表示的化合物，可以列举如2-氨基乙基磺酰胺、2-苯胺基乙磺酰胺、2-(2-苯肼基)乙磺酰胺、2-(2-苯甲酰肼基)乙磺酰胺、2-(2-苯甲酰肼基)-N-乙炔基乙磺酰胺、2-(2-苯甲酰肼基)-N-乙炔基-N-丙基乙磺酰胺、2-(2-苯甲酰肼基)-N-苄基-N-乙炔基乙磺酰胺等。
本公开所述的制备方法，其中所述水相单体为选自哌嗪、2-甲基哌嗪、聚乙烯亚胺、间苯二胺、对苯二胺、邻苯二胺和均苯三胺中的至少一种。
优选地，以所述水相溶液的总质量计，所述水相单体的质量百分比浓度为0.1～3.0wt％，更优选地为0.5～1.5wt％。如果水相单体的含量低于0.1wt％，则会导致成膜性较差，制备的纳滤膜不具备分离性能；如果水相单体的含量高于3.0wt％，则制备的纳滤膜的聚酰胺功能层较厚，严重增加了水分子的传质阻力，导致膜的性能较差。
在所述水相溶液中还可以任选地包含pH调节剂以将溶液的pH值调节至9～12的范围内，从而更有利于界面聚合反应的进行。所述pH调节剂可以为选自氢氧化钠、磷酸氢钾、氢氧化钾、碳酸钠、三乙胺/樟脑磺酸中的至少一种。其中三乙胺和樟脑磺酸组合使用用于调节pH，这样可以使反应相对温和一些，是界面聚合反应中常见的pH调节搭配。
对于基膜与水相溶液的接触时间和接触温度没有特别限定，优选在15～45℃的温度范围内接触10～60秒。
本公开所述的制备方法，其中所述油相单体为选自均苯三甲酰氯、氰脲酰氯、丹磺酰氯、间苯二甲酰氯、对苯二甲酰氯、邻苯二甲酰氯和联苯四酰氯中的至少一种。
优选地，以所述油相溶液的总质量计，所述油相单体的质量百分比浓度为 0.05～1.0wt％，更优选地为0.1～0.5wt％。如果油相单体的含量低于0.05wt％，则无法形成聚酰胺功能层以满足纳滤膜性能需求；如果油相单体的含量高于1.0wt％，则制备的纳滤膜的通量下降严重，甚至没有通量。
对于所述油相溶液中的溶剂没有特别限制，可以列举如正己烷、正庚烷、环己烷、乙基环己烷、Isopar M、Isopar H、Isopar L、Isopar E、Isopar G等。
对于基膜与油相溶液的接触时间和接触温度没有特别限定，优选在15～45℃的温度范围内接触10～60秒。
在本公开所述的制备方法中，优选地，在依次与水相溶液和油相溶液接触以进行界面聚合反应之后，可以进行加热使聚酰胺功能层进一步交联，优选地，加热温度在25～40℃的范围内，加热时间为1～5分钟。加热的目的是进一步促进溶剂的挥发和聚酰胺功能层的交联固化，如果加热温度过高或者加热时间过长则会导致膜表面的微结构被撕裂，导致膜的脱盐性能降低。
本公开所述的制备方法，所述后处理包括羟基化处理和交联处理，所述羟基化处理是指将所述油相溶液中未进行界面聚合反应的油相单体进行羟基化，其中所述羟基化处理在包含醇胺类物质的溶液中进行，优选地，所述醇胺类物质为选自二乙醇胺、三乙醇胺中的至少一种，其作用是诱导未参加界面聚合反应的酰氯类单体的酰氯基团进行羟基化改性，从而在膜的表面引入羟基基团。
在该处理中，醇胺类物质与未反应的酰氯基团进行共价结合，使得醇胺中的氨基被反应，膜表面留下羟基，由此增强膜表面的亲水性并且使得膜在长期运行过程中受到的污染得到缓解，减少了由于污染导致的膜的性能的降低。
同时，由于水相溶液中的糖苷化磺酰胺类化合物的反应活性比水相单体低，因此，糖苷化磺酰胺类化合物不是以化学键的方式与聚酰胺功能层结合，在膜的长期运行过程中，糖苷化磺酰胺类化合物会脱落，导致膜的抗菌稳定性能受损。通过在膜的表面引入羟基基团，膜内存在的糖苷化磺酰胺类化合物与膜表面的羟基通过在交联剂的作用下结合起来，通过化学键合的方式固定在聚酰胺功能层中，确保了膜在使用过程中的抗菌稳定性。
优选地，以所述包含醇胺类物质的溶液的总质量计，醇胺类物质的质量百分比浓度 为0.5～5.0wt％，当在该浓度范围内时，能够使得未进行界面聚合反应的油相单体(酰氯单体)未被全部羟基化，未被羟基化的酰氯单体被水解产生羧基，使得膜表面带负电荷，与带负电荷的染料和无机盐等产生排斥作用，从而促进对染料和无机盐进行截留。更优选地，醇胺类物质的质量百分比浓度为1.0～3.0wt％。
进一步更优选的，在40～60℃的温度范围内，在包含醇胺类物质的溶液中浸入0.5～5分钟。
在所述包含醇胺类物质的溶液中还可以任选地包含pH调节剂以将溶液的pH值调节至9～11的范围内，从而更有利于反应的进行。所述pH调节剂可以为选自氢氧化钠、磷酸氢钾、氢氧化钾、碳酸钠、三乙胺/樟脑磺酸中的至少一种。
本公开所述的制备方法，所述交联处理在包含交联剂的溶液中进行，在该处理中，通过交联剂的作用，使得通过上述的羟基化改性而留在膜的表面上的羟基与糖苷化磺酰胺类化合物的羟基、氨基进行进一步的交联固定，从而使得糖苷化磺酰胺类化合物稳定地存在于聚酰胺功能层，以确保膜在长期运行过程中的性能稳定。
优选地，所述交联剂为碳原子数为2至6的二醛类化合物。可以列举如乙二醛、丙二醛、丁二醛、戊二醛等。
优选地，以所述包含交联剂的溶液的总质量计，交联剂的质量百分比浓度为0.01～0.5wt％，更优选为0.02～0.1wt％。
优选地，在包含交联剂的溶液中的浸入时间为1～5分钟，更优选为2～4分钟。该过程主要是为了进一步增益和保证纳滤膜的性能，如果交联剂的浓度过低或浸入时间不足，会导致效果达不到预期，如果交联剂的浓度过高或浸入时间过久，同样会导致膜整体性能的降低。
本公开所述的制备方法，优选地，后处理还可以包括两阶段的水洗，第一阶段水洗温度为40～60℃，第二阶段水洗温度为20～30℃，以洗去未反应的胺类单体、酰氯类单体、糖苷化磺酰胺类化合物、交联剂等前述过程的残留物。
优选地，接着对纳滤膜表面涂覆保护层溶液，所述保护层溶液包含多羟基聚合物，所述多羟基聚合物列举如聚乙烯醇、聚乙二醇等。保护层溶液的作用是减少纳滤膜表面在后续的加热干燥处理过程中的损伤，确保膜结构的稳定性。优选地，基于所述保护层 溶液的总质量，所述多羟基聚合物的含量为1～3wt％，更优选为1.5～2.5wt％，进一步优选地，涂覆时间为5～20秒。
在所述保护层溶液中任选地可以包含选自盐酸、戊二醛中的至少一种，其中盐酸的加入主要目的是调节溶液pH值，促进所述多羟基聚合物举如聚乙烯醇、聚乙二醇等的溶解，加入少量戊二醛可以促进所述多羟基聚合物举如聚乙烯醇、聚乙二醇等的自我交联，在涂覆时，能够更好的形成保护层。
优选地进行加热干燥后处理得到最终的纳滤膜。优选地，加热烘干温度范围为50～90℃，烘干时间为1～3分钟。
作为本公开的纳滤膜的制备方法，其非限制性实例如下：
将聚砜或聚醚砜(15-25wt％)作为聚合物溶解于二甲基甲酰胺(DMF)或二甲基乙酰胺(DMAC)中，任选地添加2wt％聚乙二醇400，在60℃下搅拌6h直到聚合物完全溶解，静置脱泡；将铸膜液在无纺布上经液-固相转化法形成基膜。
将制备的基膜浸泡于包含0.1～3.0wt％水相单体、0.001～1.0wt％糖苷化磺酰胺类化合物和0～0.1wt％氢氧化钠的水相溶液中，沥干表面水珠。
接着浸入包含0.05～1.0wt％酰氯类单体的油相溶液中，沥干表面溶液。
接着依次浸入包含0.1～5.0wt％二乙醇胺的水溶液、包含0.01～0.5wt％交联剂的水溶液。
取出后用纯水洗涤，涂覆保护层溶液，然后烘干，制得具有疏松结构的且具有抗菌性能的功能层的纳滤膜。
本公开还提供根据本公开所述的制备方法制备的纳滤膜。采用本公开的制备方法制备的纳滤膜具有高达80～120L/(m 2/h)的水通量，对于刚果红、甲基橙、酸性品红的脱除率分别可以达到99％、82～90％、90～95％，对于硫酸镁的脱除率可以调节至30％，从而实现对于有机染料分子和无机盐离子的选择性分离，此外还具有优异的抗菌性能，有效地缓解了在运行过程中在膜的表面上的微生物污染。所述纳滤膜可以应用于水处理、染料、生物化工、食品、环保等领域的分离和浓缩技术。
实施例
下面结合实施例对本公开的技术方案作进一步的详细说明，但不作为对本公开的限 制。需要说明的是，本公开实施例中采用的试剂和原料除非特别说明，皆为商购可得的常规产品。
制备例
糖苷类磺酰胺类化合物的合成
(1)具有由式I表示的糖苷类磺酰胺类化合物的合成
称取28.4g磷酸氢二钠溶于100ml水中，加水稀释至1000ml备用；称取24g磷酸二氢钠溶于100ml水中，加水稀释至1000ml备用；称取68.5ml磷酸二氢钠的水溶液和31.5ml磷酸氢二钠的水溶液置于烧杯中，混合均匀配制pH值为6.5的磷酸盐缓冲溶液，备用。
称取4.3g的3-氨基苯磺酰胺置于上述磷酸盐缓冲溶液中，加热至40℃后，在搅拌的同时缓慢加入4.5g葡萄糖，在40℃下恒温搅拌5h，直到反应成为稳态；采用高效液相色谱对反应物进行纯化，采取C18为反向柱，乙腈/水(比例15/85(v/v))为流动相，流速为5ml/min，室温下进行洗脱分离，将分离得到的液体进行冷冻干燥后得到的白色结晶物即为化合物1-1。
将上述3-氨基苯磺酰胺分别替换为对氨基苯磺酰胺、2-氨基苯酚-4磺酰胺和4-氨基-N-甲基苯磺酰胺，分别合成化合物1-2、1-3和1-4；
将上述葡萄糖分别替换为N-芳基糖苷、N-乙酰-D-氨基葡萄糖和N-乙酰-D-半乳糖胺，分别合成化合物1-5、1-6和1-7。
(2)具有由式II表示的糖苷类磺酰胺类化合物的合成
称取5.9g正丙胺、30.3g三乙胺和13.5g二氯甲烷置于100ml烧瓶中，将烧瓶置于冰浴环境中，在搅拌的同时缓慢加入24.5g 2-氯乙基磺酰氯，在室温下反应两小时，用水和二氯甲烷进行萃取，取有机相溶液，采用旋转蒸发器进行真空旋干，通过液相色谱硅胶柱分离，以石油醚/乙酸乙酯(比例80/20(v/v))为流动相，流速为5ml/min，在室温下进行洗脱分离，经纯化得到中间产物化合物A。
称取2.1g得到的化合物A溶于7.9g乙腈中，在搅拌过程中依次加入12.5g 3-溴丙炔和27g碳酸钾，在95℃下的油浴环境中加热(含回流装置)，反应5～6小时后，取出混合液体进行抽滤，将得到的液体通过旋转蒸发器真空旋干，通过液相色谱硅胶柱分离，以石油 醚/乙酸乙酯(比例90/10(v/v))为流动相，流速为5ml/min，在室温下进行洗脱分离，经纯化得到中间产物化合物B。
(a)由式II表示的糖苷类磺酰胺类化合物中分子式中含有苯环的化合物的合成
称取18.7g中间产物化合物B溶解于30ml甲醇中，加入20.4g苯甲酰肼，在搅拌的同时在室温下反应24小时，反应完成后通过旋转蒸发器将溶剂减压旋干，然后通过液相色谱硅胶柱分离，以石油醚/乙酸乙酯(比例50/50(v/v))为流动相，流速为5ml/min，在室温下进行洗脱分离，经纯化得到中间产物化合物C。
配制甲醇/冰醋酸体积比为85:15的混合溶剂，称取2g中间产物化合物C和1.3g D-葡萄糖溶解于5ml该混合溶剂中，在45℃水浴环境中搅拌12小时，产物通过旋转蒸发器将溶剂减压旋干，然后通过液相色谱硅胶柱分离，以二氯甲烷/甲醇(比例92/8(v/v))为流动相，流速为5ml/min，室温下进行洗脱分离，经纯化得到化合物2-1。
称取2g中间产物化合物C和1.1g D-核糖溶解于5ml上述甲醇/冰醋酸混合溶剂中，在45℃水浴环境中搅拌12小时，产物通过旋转蒸发器将溶剂减压旋干，然后通过液相色谱硅胶柱分离，以乙酸乙酯为流动相，流速为5ml/min，室温下进行洗脱分离，经纯化得到化合物2-2。
称取2g中间产物化合物C和1.5g N-乙酰-D-氨基葡萄糖溶解于5ml上述甲醇/冰醋酸混合溶剂中，在45℃水浴环境中搅拌12小时，产物通过旋转蒸发器将溶剂减压旋干，然后通过液相色谱硅胶柱分离，以二氯甲烷/甲醇(比例92/8(v/v))为流动相，流速为5ml/min，室温下进行洗脱分离，经纯化得到化合物2-3。
(b)由式II表示的糖苷类磺酰胺类化合物中分子式中不含有苯环的化合物的合成
称取18.7g中间产物化合物B溶解于30ml甲醇中，加入9.7g乙酰肼，在搅拌的同时在室温下反应24小时，反应完成后通过旋转蒸发器将溶剂减压旋干，然后通过液相色谱硅胶柱分离，以石油醚/乙酸乙酯(比例50/50(v/v))为流动相，流速为5ml/min，在室温下进行洗脱分离，经纯化得到中间产物化合物D。
配制甲醇/冰醋酸体积比为85:15的混合溶剂，称取2g中间产物化合物D和1.3g D-葡萄糖溶解于5ml该混合溶剂中，在45℃水浴环境中搅拌12小时，产物通过旋转蒸发器将溶剂减压旋干，然后通过液相色谱硅胶柱分离，以二氯甲烷/甲醇(比例91/9(v/v))为流动相， 流速为5ml/min，在室温下进行洗脱分离，经纯化得到化合物3-1。
称取2g中间产物化合物D和1.4g D-核糖溶解于5ml上述甲醇/冰醋酸混合溶剂中，在45℃水浴环境中搅拌12小时，产物通过旋转蒸发器将溶剂减压旋干，然后通过液相色谱硅胶柱分离，以乙酸乙酯为流动相，流速为5ml/min，在室温下进行洗脱分离，经纯化得到化合物3-2。
称取2g中间产物化合物D和1.5g N-乙酰-D-氨基葡萄糖溶解于5ml上述甲醇/冰醋酸混合溶剂中，在45℃水浴环境中搅拌12小时，产物通过旋转蒸发器将溶剂减压旋干，然后通过液相色谱硅胶柱分离，以二氯甲烷/甲醇(比例92/8(v/v))为流动相，流速为5ml/min，在室温下进行洗脱分离，经纯化得到化合物3-3。
基膜的制备
基膜采用浸没沉淀法进行制备，在铸膜液中包含18wt％聚砜和2wt％聚乙二醇400，其中溶剂为N,N-二甲基甲酰胺，在温度为60℃下搅拌6小时后放入25℃环境中恒温脱泡12小时；将脱泡后的铸膜液通过刮膜机刮制于聚酯PET无纺布上，基膜厚度为40μm，浸入温度为15℃的纯水冷水浴中固化成膜，通过水洗得到具有多孔结构的聚砜支撑层基膜。
水相溶液的制备
取哌嗪10g溶于990g纯水中，采用0.1mol/L的氢氧化钠溶液调节pH值为11，制备水相溶液。
油相溶液的制备
取均苯三甲酰氯2g溶于998g的Isopar G溶剂中制备油相溶液。
二乙醇胺溶液的制备
按照二乙醇胺为3wt％、三乙胺为2wt％、樟脑磺酸为4wt％，余量为纯水来制备二乙醇胺溶液。
交联剂溶液的制备
取戊二醛浓度为40wt％的水溶液1.25g溶于100g纯水中，然后加水稀释至1000g，滴加硫酸以调节pH为2.5～3.5。
聚乙烯醇溶液的制备
称取10g聚乙烯醇粉末、1g盐酸浓度为37wt％的水溶液和2g戊二醛浓度为40wt％的水溶液置于455g的水中，在90℃下搅拌0.5小时，加入500g常温纯水稀释，备用。
比较例1
将上述制备的聚砜基膜在纯水溶液中浸泡5分钟确保膜面的润湿，然后浸入到水相溶液中，浸入时间为30秒，取出后去除膜表面多余的溶液后，浸入到油相溶液中进行界面聚合反应生成聚酰胺功能层，反应时间为30秒；在30℃烘箱中进行热处理进一步促使交联，加热处理时间为2分钟得到初生纳滤膜。分别进行50℃热水洗涤2分钟和25℃冷水洗涤3分钟和涂覆聚乙烯醇溶液保护层，涂覆温度25℃，涂覆时间10秒，在85℃下干燥1.5分钟得到纳滤膜。
比较例2
除了得到初生纳滤膜后，分别浸入50℃二乙醇胺溶液中进行处理2分钟，和在常温下浸入交联剂溶液中处理2分钟以外，以与比较例1相同的方式进行比较例2。
实施例1
除了在水相溶液中添加有1g以上合成的糖苷化磺酰胺类化合物1-1以外，以与比较例2相同的方式进行实施例1。
比较例3
除了在水相溶液中添加有1g以上合成的糖苷化磺酰胺类化合物1-1以外，以与比较例1相同的方式进行比较例3。
实施例2至13
除了将糖苷化磺酰胺类化合物1-1分别替换为以上合成的糖苷化磺酰胺类化合物1-2、1-3、1-4、1-5、1-6、1-7、2-1、2-2、2-3、3-1、3-2、3-3以外，以与实施例1相同的方式进行实施例2至13。
性能表征与测试结果
(1)渗透分离性能测试
将比较例1至3和实施例1至13中得到的纳滤膜，分别在错流式膜片检验台上测试，测试条件为0.1g/L的染料+1g/L的硫酸镁水溶液(其中染料分别为刚果红、甲基橙和酸性品红，测试过程中分别对三种染料和硫酸镁的混合溶液测试)，70psi操作压力，温度25℃，pH值7。测试稳定时间40分钟。
测试结果如下表1所示：
表1
Figure PCTCN2022132633-appb-000005
Figure PCTCN2022132633-appb-000006
根据比较例1至2的结果可知，由于未添加糖苷化磺酰胺类化合物，无论是否进行羟基化处理和交联处理，所得的膜在渗透通量以及对于有机染料分子和无机盐离子的选择性分离方面差别不大；根据比较例3和实施例1至3的结果可知，通过在水相溶液中加入糖苷化磺酰胺类化合物作为添加剂参与界面聚合反应，所制备的纳滤膜的渗透通量得到显著的提升；同时，膜对有机染料分子和无机盐离子的选择性增加，这有利于用于有机染料分子与无机盐离子的选择性分离，可有效地应用于染料行业的废水处理中。
此外，在测试过程中，观察到在比较例3中，在测试稳定时间内存在选择性分离性能逐渐降低的过程，而在实施例1至13中，未观察到选择性分离性能的明显降低。通过比较例3与实施例1至13的对比可知，对于添加有糖苷化磺酰胺类化合物的纳滤膜来说，通过进行羟基化处理和交联处理，能够有效地固定添加剂糖苷化磺酰胺类化合物，确保膜不出现大的缺陷而导致分离性能的降低。
(2)抗菌性测试
培养基的制备：将5.0g牛肉膏、10.0g蛋白胨和5.0g NaCl溶于1L纯水中，搅拌均匀后，调节pH值为中性。然后，在温度为120℃的高压釜中灭菌20分钟得到液体培养基。在液体培养基中加18g琼脂，灭菌得到固体培养基。
采用大肠杆菌(ATCC：25922)和金黄色葡萄球菌(CMCC(B)：26003)的菌落计数法研究纳滤膜的抗菌性能。
首先，将细菌在37℃的液体培养基中培养24小时，取带细菌的培养基连续振荡，离心得到细菌细胞，并用PBS稀释。其次，将面积为3cm×3cm的膜样品浸入15mL细菌悬浮液中，15小时后取出。然后，将稀释为0.1mL的细菌悬浮液均匀涂覆在固体培养基上，然后在37℃下培育24小时。最后，计数固体培养基上的菌落数。所有操作均在无菌环境进行。生长细菌数量按以下公式计算：
Figure PCTCN2022132633-appb-000007
式中：ABA为抗菌活性；
Np为在聚砜基膜上生长的菌落数；
Ns为在纳滤膜上生长的菌落数；
取上述比较例2和实施例1、4、7、10、11中的纳滤膜进行抗菌测试。测试结果如表2：
表2
Figure PCTCN2022132633-appb-000008
从表2的结果可见，含有添加剂糖苷化磺酰胺类化合物的膜具备优异的抗菌活性，这有利于膜在运行过程中有效地缓解膜表面的生物污染。
产业上的可利用性
本公开提供了一种纳滤膜的制备方法，该方法简单、易于操作。采用本公开的制备方法制备的纳滤膜具有高达80～120L/(m 2/h)的水通量，对于刚果红、甲基橙、酸性品红的脱除率分别可以达到99％、82～90％、90～95％，对于硫酸镁的脱除率可以调节至30％，从而实现对于有机染料分子和无机盐的选择性分离，此外还具有优异的抗菌性能，有效地缓解了在运行过程中在膜的表面上的微生物污染。本公开提供的纳滤膜可以应用于水处理、染料、生物化工、食品、环保等领域进行有效的选择性分离。

Claims (10)

  1. 一种纳滤膜的制备方法，其特征在于，包括以下步骤：
    制备铸膜液，使所述铸膜液在增强材料上固化形成基膜，其中所述铸膜液包含聚合物和溶剂；
    将所述基膜依次与水相溶液和油相溶液接触以在所述基膜上进行界面聚合反应形成聚酰胺功能层，其中所述水相溶液包含水相单体和添加剂，所述添加剂为糖苷化磺酰胺类化合物，所述油相溶液包含油相单体；
    经后处理得到纳滤膜，其中所述后处理包括羟基化处理和交联处理。
  2. 根据权利要求1所述的制备方法，其中所述聚合物为选自聚砜、聚醚砜、磺化聚醚砜、聚酰亚胺、聚偏氟乙烯、聚丙烯腈、聚丙烯和聚氯乙烯中的至少一种。
  3. 根据权利要求1或2所述的制备方法，其中所述糖苷化磺酰胺类化合物通过将糖类化合物与含磺酰胺基团的化合物进行糖苷化反应得到，优选地，基于所述水相溶液的总质量，所述糖苷化磺酰胺类化合物的质量百分比浓度为0.001～1.0wt％。
  4. 根据权利要求3所述的制备方法，其中所述糖类化合物为选自D-葡萄糖、N-芳基糖苷、乳糖、半乳糖、N-乙酰-D-氨基葡萄糖、阿拉伯糖、N-乙酰-D-半乳糖胺、D-核糖、L-鼠李糖、木糖、甘露糖和麦芽糖中的至少一种。
  5. 根据权利要求3所述的制备方法，其中所述含磺酰胺基团的化合物为选自由下式I表示的化合物和下式II表示的化合物中的至少一种：
    Figure PCTCN2022132633-appb-100001
    在式I中，R1和R2为选自H、碳原子数为1至5的烃基、氨基和氰基中的至少一种，R3、R4和R5为选自H、氨基、亚氨基和羟基中的至少一种，R3、R4和R5中至少之一为氨基；
    Figure PCTCN2022132633-appb-100002
    在式II中，R1和R2为碳原子数为1至10的烃基，所述碳原子数为1至10的烃基任选地含有选自氨基、氰基、羧基、双键和乙炔基中的至少一种，R3为碳原子数为1至5的烃基，R4为选自H、碳原子数为1至10的烃基中的至少一种，所述碳原子数为1至10的烃基任选地含有选自羟基、羧基、酮基、醚键、羰基、亚氨基、酰基和苯基中的至少一种。
  6. 根据权利要求1或2所述的制备方法，其中所述水相单体为选自哌嗪、2-甲基哌嗪、聚乙烯亚胺、间苯二胺、对苯二胺、邻苯二胺和均苯三胺中的至少一种；优选地，以所述水相溶液的总质量计，所述水相单体的质量百分比浓度为0.1～3.0wt％。
  7. 根据权利要求1或2所述的制备方法，其中所述油相单体为选自均苯三甲酰氯、氰脲酰氯、丹磺酰氯、间苯二甲酰氯、对苯二甲酰氯、邻苯二甲酰氯和联苯四酰氯中的至少一种；优选地，以所述油相溶液的总质量计，所述油相单体的质量百分比浓度为0.05～1.0wt％。
  8. 根据权利要求1或2所述的制备方法，其中所述羟基化处理在包含醇胺类物质的溶液中进行，优选地，所述醇胺类物质为选自二乙醇胺、三乙醇胺中的至少一种，优选地，以所述包含醇胺类物质的溶液的总质量计，醇胺类物质的质量百分比浓度为0.5～5.0wt％。
  9. 根据权利要求1或2所述的制备方法，其中所述交联处理在包含交联剂的溶液中进行，所述交联剂为碳原子数为2至6的二醛类化合物，优选地，以所述包含交联剂的溶液的总质量计，交联剂的质量百分比浓度为0.01～0.5wt％。
  10. 一种根据权利要求1-9任一项所述的制备方法制备的纳滤膜。
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