CN115569536A - Anti-pollution ultrafiltration membrane and preparation method and application thereof - Google Patents
Anti-pollution ultrafiltration membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an anti-pollution ultrafiltration membrane as well as a preparation method and application thereof, belonging to the technical field of membrane separation, wherein the preparation method of the anti-pollution ultrafiltration membrane comprises the following steps: (1) Carrying out amination modification on the polymer powder to obtain amination modified polymer powder; (2) Preparing a membrane casting solution by using aminated modified polymer powder, carrying out curtain coating on the membrane casting solution on a supporting layer to form a membrane, transferring the membrane casting solution to a coagulating bath for curing and forming to obtain a wet membrane, and further washing and airing to obtain an amino-containing ultrafiltration membrane; (3) Taking an epoxy monomer, a zwitterionic monomer and an initiator as raw materials to carry out polymerization reaction to prepare an epoxy-zwitterionic copolymer; (4) And (3) grafting an epoxy-zwitterionic copolymer onto the amino-containing ultrafiltration membrane obtained in the step (2) through an epoxy ring-opening reaction to obtain the anti-pollution ultrafiltration membrane. The anti-pollution ultrafiltration membrane prepared by the method has good hydrophilicity, excellent protein pollution resistance and bacteria adhesion resistance, and can maintain higher pure water flux.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to an anti-pollution ultrafiltration membrane as well as a preparation method and application thereof.
Background
The membrane separation technology can effectively intercept pollutants, bacteria and pathogenic bacteria, has the advantages of high efficiency, energy conservation, environmental protection, simple filtration process, easy control and the like, and becomes one of the technologies with development potential in the fields of water treatment, hemodialysis and the like. The membrane can be divided into a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane and the like in the application process, wherein the minimum cut-off molecular weight of the ultrafiltration membrane is 2000 daltons, and the ultrafiltration membrane can be used for separating proteins, enzymes, nucleic acids, polysaccharides, polypeptides, antibiotics, viruses and the like. The ultrafiltration membrane has no phase transfer in the use process, does not need to add any toxic and harmful chemical substances, and has wide application.
In the use process of the ultrafiltration membrane, the deposition or adsorption of various pollutants can cause the serious reduction of the membrane flux, and the application cost is increased, so that the improvement of the anti-pollution capability of the ultrafiltration membrane is one of the problems which need to be solved urgently in the prior art. From the pollutant source division, membrane pollution mainly includes inorganic pollution, organic pollution and biological pollution. Among them, biological contamination is a common problem in the fields of ultrafiltration membrane water treatment and hemodialysis, and inhibition of protein contamination and bacterial adhesion is an important way to control biological contamination. In order to solve the pollution problem of the ultrafiltration membrane in the using process, the commonly used methods mainly comprise raw material treatment, membrane separation process optimization, membrane cleaning, development of an anti-pollution membrane and the like, wherein other operations are required to be introduced in the first three methods, the cost is increased, the membrane pollution cannot be radically treated, the anti-pollution membrane is developed to inhibit the interaction between a pollution source and a membrane material, and the method is a fundamental method for solving the membrane pollution.
Chinese patent publication No. CN112316754A discloses a method for preparing an anti-pollution hollow fiber ultrafiltration membrane: adding magnetic nanoparticles into the membrane casting solution by a blending method, and then spinning to prepare the anti-pollution hollow fiber ultrafiltration membrane, wherein the magnetic nanoparticles in the membrane casting solution account for 0.1-5% by weight; the hollow fiber ultrafiltration membrane prepared by the method has magnetism, can swing under the action of a magnetic field, and is beneficial to cleaning pollutants from the surface of the membrane wire and the inside of the hollow part, but the magnetic nanoparticles blended and doped by the method have the risk of falling off in the preparation and use processes of the membrane, possibly cause secondary pollution, and are not suitable for long-term use.
Chinese patent publication No. CN108579438A discloses a preparation method of a large-flux anti-pollution polyvinyl chloride ultrafiltration membrane, which comprises the steps of mixing a polymer with an organic solvent, heating and activating under the protection of nitrogen, adding an amphiphilic block copolymer, continuously stirring to completely dissolve the polymer and the amphiphilic block copolymer, and finally standing and defoaming to obtain a membrane casting solution; dissolving inorganic salt in deionized water to obtain a coagulating bath; and pouring the membrane casting solution onto a glass flat plate, leveling the glass flat plate by using a scraper, immersing the glass flat plate with the membrane casting solution into a coagulating bath, and taking out the glass flat plate after gelation to obtain the large-flux anti-pollution polyvinyl chloride ultrafiltration membrane. The method introduces the anti-pollution substances through the stirring process, so that the anti-pollution substances are very easy to wrap in the film preparation process, and the anti-pollution efficiency is reduced.
Disclosure of Invention
The invention provides a preparation method of an anti-pollution ultrafiltration membrane, which has the advantages of simple process, low equipment requirement, mild reaction condition, good hydrophilicity of the prepared anti-pollution ultrafiltration membrane, excellent protein pollution resistance and bacteria adhesion resistance, and capability of maintaining higher pure water flux.
The technical scheme is as follows:
a preparation method of an anti-pollution ultrafiltration membrane comprises the following steps:
(1) Carrying out amination modification on the polymer powder to obtain amination modified polymer powder;
(2) Preparing a membrane casting solution by using the aminated modified polymer powder in the step (1), carrying out curtain coating on the membrane casting solution on a support layer to form a membrane, transferring the membrane casting solution to a coagulating bath to carry out curing molding to obtain a wet membrane, and washing and airing the wet membrane to obtain an amino-containing ultrafiltration membrane;
(3) Taking an epoxy monomer, a zwitterionic monomer and an initiator as raw materials to perform polymerization reaction to prepare an epoxy-zwitterionic copolymer;
(4) And (3) grafting the epoxy-zwitterionic copolymer to the amino-containing ultrafiltration membrane obtained in the step (2) through an epoxy ring-opening reaction to obtain the anti-pollution ultrafiltration membrane.
According to the invention, polymer powder is aminated, and an amino-containing ultrafiltration membrane is prepared by phase inversion of an aminated polymer solution; then, carrying out an epoxy ring-opening reaction on amino on the amino-containing ultrafiltration membrane and the epoxy-zwitterionic copolymer so as to graft a zwitterionic polymer on the amino-containing ultrafiltration membrane, thus preparing the anti-pollution ultrafiltration membrane; the epoxy-zwitter-ion copolymer is connected with the amino-containing ultrafiltration membrane through a covalent bond, the binding force is strong, and the grafted zwitter-ion polymer simultaneously has positive and negative electric groups, so that a hydration layer is easily formed, and the hydration layer has strong hydration action, thereby having the capability of resisting protein pollution. The method has low requirement on equipment, the preparation method is simple, the improvement is convenient on the basis of the traditional ultrafiltration membrane preparation process, the amplification production is realized, the obtained anti-pollution ultrafiltration membrane has good hydrophilicity and excellent protein pollution resistance, can maintain higher pure water flux, has good antibacterial adhesion capability, and has wide prospects in the fields of water treatment, hemodialysis and the like.
The polymer powder comprises polysulfone, polyethersulfone, polyacrylonitrile, polyvinylidene fluoride, polyvinyl chloride or polyimide and the like.
Preferably, in the step (1), the polymer powder is placed in an aqueous solution of amino monomer for amination modification; the amino monomer is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine.
Further preferably, the concentration of the aqueous amino monomer solution is 5 to 20wt%; the temperature of amination modification is 80-180 ℃, and the time is 20-70h.
The invention carries out amination modification on the polymer powder and utilizes the amination modified polymer powder to prepare the membrane, the amination modification degree is high, the membrane thickness, the pore diameter and other parameters are easy to adjust, and the membrane preparation parameters can be adjusted according to the product requirements.
Preferably, in the step (2), the casting solution is an amination modified polymer powder solution with the concentration of 15-25wt%, and the solvent is at least one selected from acetone, N-dimethylformamide, tetrahydrofuran, N-dimethylacetamide and N-methylpyrrolidone;
preferably, in the step (2), the coagulation bath is water, methanol or ethanol, and the temperature of the coagulation bath is 20-50 ℃.
The synthesis and grafting of the epoxy-zwitterionic copolymer are the key points for preparing the anti-pollution ultrafiltration membrane, and in the step (3), the epoxy monomer is at least one of glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether and allyl alcohol glycidyl ether; the zwitterionic monomer is at least one of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate and 2-methacryloyloxyethyl phosphorylcholine, and the initiator is at least one of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile and dibenzoyl peroxide.
Preferably, in the polymerization reaction system, the molar ratio of the epoxy monomer to the zwitterionic monomer is 1:9-9:1, the amount of the initiator is 1-8mol% of the total amount of the epoxy monomer and the zwitterion monomer.
The polymerization reaction time is 3-10h, and the temperature is 50-90 ℃.
Specifically, in the step (3), an epoxy monomer, a zwitterionic monomer and an initiator are mixed, the mixture is heated and stirred at 50-90 ℃ for reaction for 3-10 hours to obtain a crude product solution, the crude product solution is dripped into absolute ethyl alcohol to obtain a precipitate, and the precipitate is dissolved in water and is freeze-dried to obtain the epoxy-zwitterionic copolymer.
The structural formula of the epoxy-zwitter-ion copolymer is represented as follows:
wherein R is 1 Is the residue of said zwitterionic monomer, R 2 M and n are positive integers of 1-100, which are the residues of the epoxy monomers.
Preferably, the number average molecular weight of the epoxy-zwitterionic copolymer is 20000-30000.
Preferably, in the step (4), the epoxy ring-opening reaction comprises the following specific steps: and (2) placing the amino-containing ultrafiltration membrane in an epoxy-zwitter-ion copolymer solution for grafting reaction, wherein the grafting reaction temperature is 50-90 ℃, and the grafting reaction time is 6-24h.
Further preferably, the concentration of the epoxy-zwitterionic copolymer solution is 5-30mg/mL; the hydrophilicity of the product membrane produced in the above preferred concentration range is excellent.
The catalyst for the epoxy ring-opening reaction is one of triethylamine solution, dodecyl trimethyl ammonium chloride solution, dodecyl dimethyl benzyl ammonium bromide solution, pyridine solution, potassium hydroxide solution or sodium hydroxide solution.
The invention also provides the anti-pollution ultrafiltration membrane prepared by the preparation method of the anti-pollution ultrafiltration membrane; the anti-pollution ultrafiltration membrane comprises an amino-containing ultrafiltration membrane and an epoxy-zwitterionic copolymer grafted on the amino-containing ultrafiltration membrane.
The invention also provides application of the anti-pollution ultrafiltration membrane in the technical field of membrane separation. The anti-pollution ultrafiltration membrane has excellent protein pollution resistance and bacteria adhesion resistance, can maintain high pure water flux, and can be applied to the aspects of water treatment or hemodialysis and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, under the action of an initiator, an epoxy monomer and a zwitterionic monomer are subjected to free radical polymerization to synthesize an epoxy-zwitterionic copolymer, and then zwitterions are anchored on an amino-containing ultrafiltration membrane through an epoxy ring-opening reaction, the epoxy-zwitterionic copolymer and the amino-containing ultrafiltration membrane are connected through covalent bonds, so that the binding force is strong, the constructed modified layer is more stable than non-covalent modification methods such as surface coating, blending and doping, and the risk of falling off of the modified layer in long-term use is avoided.
(2) The amino-containing ultrafiltration membrane is prepared by using amination modified polymer powder, the raw material polymer powder is modified, and the whole process of preparing the ultrafiltration membrane by using a phase inversion method is optimized, so that the graft sites of the anti-pollution medium are uniformly distributed, the anti-pollution modification is easy, the modification effect is good, and the property and the structure of the ultrafiltration membrane are convenient to regulate and control.
(3) According to the invention, the epoxy-zwitter-ion copolymer is grafted to the amino-containing ultrafiltration membrane, so that the prepared anti-pollution ultrafiltration membrane has good protein pollution resistance and bacterial adhesion resistance, is good in hydrophilicity, has a water contact angle of 33 degrees at the lowest, and can maintain high pure water flux.
(4) The anti-pollution ultrafiltration membrane provided by the invention has the advantages of simple preparation method, low equipment requirement, easiness in storage, long service life, low preparation cost, no toxic and harmful substance residue, convenience in realizing amplified preparation production and wide prospect in the fields of water treatment and hemodialysis.
Drawings
Fig. 1 is a graph showing the XPS analysis results of the anti-contamination ultrafiltration membrane of example 3 and the amino-containing ultrafiltration membrane of comparative example 1, wherein a is the amino-containing polyethersulfone membrane of comparative example 1, and B is the anti-contamination polyethersulfone membrane of example 3.
FIG. 2 is a graph comparing the water contact angle of the anti-fouling ultrafiltration membrane of example 3 with that of the amino-containing ultrafiltration membrane of comparative example 1.
FIG. 3 is a graph showing the flux-time change in the filtration of 1g/L bovine serum albumin solution by the anti-contamination ultrafiltration membrane of example 3 and the amino group-containing ultrafiltration membrane of comparative example 1.
FIG. 4 is a scanning electron microscope image of the adhesion of the anti-fouling ultrafiltration membrane of example 3 and the amino group-containing ultrafiltration membrane of comparative example 1 in Escherichia coli, wherein A is the amino group-containing polyethersulfone membrane of comparative example 1, and B is the anti-fouling polyethersulfone membrane of example 3.
Detailed Description
The invention will be further elucidated with reference to the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Zwitterionic monomers 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate (CAS number: 24249-95-4), 2-methacryloyloxyethyl phosphorylcholine (CAS number: 67881-98-5), and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide (CAS number: 3637-26-1) were all purchased from Shanghai-derived leaf Biotech, inc.
Example 1
(1) Putting polysulfone powder into 5wt% of ethylenediamine aqueous solution, carrying out heat treatment for 70h at 80 ℃, taking out the powder after amination reaction is finished, sequentially washing the powder with absolute ethyl alcohol and ultrapure water for three times, and naturally airing to obtain aminated modified polysulfone powder;
(2) Placing the aminated modified polysulfone powder into acetone, stirring and dissolving to obtain a membrane casting solution with the concentration of 15wt%, standing and defoaming, casting and blade-coating the membrane casting solution on a polypropylene non-woven fabric support layer by using a scraper, then quickly transferring the membrane casting solution into ultrapure water with the temperature of 20 ℃ for curing and forming to obtain a wet membrane, placing the wet membrane into the ultrapure water for soaking and cleaning, and naturally airing to obtain an amino-containing polysulfone ultrafiltration membrane;
(3) Preparing a mixed solution of 4-hydroxybutyl acrylate glycidyl ether and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide (the content of the 4-hydroxybutyl acrylate glycidyl ether is 10 mol%), stirring uniformly, purging with nitrogen, adding azobisisobutyronitrile accounting for 1mol% of the total amount of the epoxy monomer and the zwitterionic monomer, placing the reaction system in a three-neck flask, reacting at 50 ℃ for 10 hours, dropping the crude product solution into absolute ethanol after the reaction is finished to obtain a precipitate, dissolving the precipitate in water, and freeze-drying to obtain white solid powder of the epoxy-zwitterionic copolymer, wherein the epoxy-zwitterionic copolymer is poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-4-hydroxybutyl acrylate glycidyl ether);
(4) And (2) placing the amino-containing polysulfone ultrafiltration membrane into 5mg/mL poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-4-hydroxybutylacrylate glycidyl ether) solution, then adding 100 mu L pyridine solution into each mL poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-4-hydroxybutylacrylate glycidyl ether) solution, reacting at 50 ℃ for 24h, taking out the membrane after the reaction is finished, washing with ultrapure water for three times, and naturally airing to obtain the anti-pollution polysulfone ultrafiltration membrane.
Example 2
(1) Putting the polyether sulfone powder into 8wt% of hexamethylenediamine aqueous solution, carrying out heat treatment for 60h at 100 ℃, taking out the powder after the amination reaction is finished, sequentially washing the powder with absolute ethyl alcohol and ultrapure water for three times, and naturally airing to obtain aminated modified polyether sulfone powder;
(2) Placing the amination modified polyether sulfone powder in N, N-dimethylformamide, stirring and dissolving to obtain a casting solution with the concentration of 17wt%, standing and defoaming, then carrying out curtain coating and blade coating on the casting solution on a polypropylene non-woven fabric supporting layer by using a scraper, then quickly transferring the casting solution to ultrapure water at 25 ℃, curing and forming to obtain a wet film, placing the wet film in the ultrapure water, soaking and cleaning, and naturally airing to obtain an amino-containing polyether sulfone ultrafiltration membrane;
(3) Preparing a mixed solution of glycidyl methacrylate and 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate (the content of the glycidyl methacrylate is 10 mol%), stirring uniformly, purging with nitrogen, then adding azodiisovaleronitrile accounting for 3mol% of the total amount of the epoxy monomer and the zwitterionic monomer, then placing a reaction system into a three-neck flask, reacting for 4 hours at 70 ℃, dropping a crude product solution into absolute ethyl alcohol after the reaction is finished to obtain a precipitate, dissolving the precipitate in water, and freeze-drying to obtain white solid powder of an epoxy-zwitterionic copolymer, wherein the epoxy-zwitterionic copolymer is poly (3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate-co-glycidyl methacrylate);
(4) Placing the amino-containing polyethersulfone ultrafiltration membrane in 7mg/mL poly (3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate-co-glycidyl methacrylate) solution, then adding 100 mu L dodecyl trimethyl ammonium chloride solution into each mL poly (3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate-co-glycidyl methacrylate) solution, reacting for 6h at 50 ℃, taking out the membrane after the reaction is finished, washing with ultrapure water for three times, and naturally airing to obtain the anti-pollution polyethersulfone ultrafiltration membrane.
Example 3
(1) Putting the polyether sulfone powder into 10wt% of diethylenetriamine aqueous solution, carrying out heat treatment for 70h at the temperature of 80 ℃, taking out the powder after the amination reaction is finished, sequentially washing the powder with absolute ethyl alcohol and ultrapure water for three times, and naturally airing to obtain aminated modified polyether sulfone powder;
(2) Putting the amination modified polyethersulfone powder into N, N-dimethylformamide, stirring and dissolving to obtain a casting solution with the concentration of 20wt%, standing and defoaming, carrying out curtain coating and blade coating on the casting solution on a polypropylene non-woven fabric supporting layer by using a scraper, then quickly transferring the casting solution into 50 ℃ ultrapure water, curing and forming to obtain a wet membrane, soaking and cleaning the wet membrane in the ultrapure water, and naturally airing to obtain an amino-containing polyethersulfone ultrafiltration membrane;
(3) Preparing a mixed solution of glycidyl methacrylate and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide (the content of the glycidyl methacrylate is 20 mol%), stirring uniformly, purging with nitrogen, then adding azobisisobutyronitrile accounting for 1mol% of the total amount of the epoxy monomer and the zwitterionic monomer, then placing a reaction system into a three-neck flask, reacting for 6 hours at 70 ℃, after the reaction is finished, dripping the crude product solution into absolute ethyl alcohol to obtain a precipitate, dissolving the precipitate in water, and freeze-drying to obtain white solid powder of an epoxy-zwitterionic copolymer, wherein the epoxy-zwitterionic copolymer is poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-glycidyl methacrylate), and the structural formula is shown in the following formula, wherein x and y are positive integers of 1-100.
(4) And (2) placing the amino-containing polyethersulfone ultrafiltration membrane into a poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-glycidyl methacrylate) solution of 30mg/mL, then adding 100 mu L of triethylamine solution into each milliliter of poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-glycidyl methacrylate) solution, reacting for 12 hours at the temperature of 60 ℃, taking out the membrane after the reaction is finished, washing with ultrapure water for three times, and naturally airing to obtain the anti-pollution polyethersulfone ultrafiltration membrane.
Example 4
(1) Placing polyacrylonitrile powder in 20wt% triethylene tetramine aqueous solution for heat treatment for 30h at 180 ℃, taking out the powder after amination reaction is finished, sequentially cleaning the powder with absolute ethyl alcohol and ultrapure water for three times, and naturally airing to obtain aminated modified polyacrylonitrile powder;
(2) Putting the aminated modified polyacrylonitrile powder into tetrahydrofuran, stirring and dissolving to obtain a casting solution with the concentration of 25wt%, standing and defoaming, carrying out curtain coating and blade coating on the casting solution on a polypropylene non-woven fabric supporting layer by using a scraper, then quickly transferring to methanol with the temperature of 40 ℃, curing and forming to obtain a wet film, soaking and cleaning the wet film in ultrapure water, and naturally airing to obtain an amino-containing polyacrylonitrile ultrafiltration membrane;
(3) Preparing a mixed solution of allyl alcohol glycidyl ether and 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate (the content of the allyl alcohol glycidyl ether is 30 mol%), stirring uniformly, purging with nitrogen, adding dibenzoyl peroxide accounting for 3mol% of the total amount of the epoxy monomer and the zwitterionic monomer, then placing a reaction system into a three-neck flask, reacting for 6 hours at 80 ℃, dropping a crude product solution into absolute ethyl alcohol after the reaction is finished to obtain a precipitate, dissolving the precipitate in water, and freeze-drying to obtain white solid powder of an epoxy-zwitterionic copolymer, wherein the epoxy-zwitterionic copolymer is poly (3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate-co-allyl alcohol glycidyl ether);
(4) Putting the amino-containing polyacrylonitrile ultrafiltration membrane into 20mg/mL poly (3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate-co-allyl alcohol glycidyl ether) solution, then adding 100 mu L sodium hydroxide solution into each milliliter of poly (3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate-co-allyl alcohol glycidyl ether) solution, reacting for 20 hours at 80 ℃, taking out the membrane after the reaction is finished, washing with ultrapure water for three times, and naturally airing to obtain the anti-pollution polyacrylonitrile ultrafiltration membrane.
Example 5
(1) Placing polyvinylidene fluoride powder in 15wt% of tetraethylenepentamine aqueous solution, carrying out heat treatment for 50h at 100 ℃, taking out the powder after amination reaction is finished, sequentially cleaning with absolute ethyl alcohol and ultrapure water for three times, and naturally drying to obtain aminated modified polyvinylidene fluoride powder;
(2) Placing the amination modified polyvinylidene fluoride powder into N, N-dimethylacetamide, stirring and dissolving to obtain a casting solution with the concentration of 18wt%, standing and defoaming, then casting and blade-coating the casting solution on a polypropylene non-woven fabric support layer by using a scraper, then quickly transferring the polypropylene non-woven fabric support layer into methanol at 40 ℃ for curing and forming to obtain a wet film, placing the wet film in ultrapure water, soaking and cleaning, and naturally airing to obtain an amino-containing polyvinylidene fluoride ultrafiltration membrane;
(3) Preparing a mixed solution of glycidyl methacrylate and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide (the content of the glycidyl methacrylate is 40 mol%), stirring uniformly, purging with nitrogen, then adding azodiisoheptanonitrile in an amount which is 3mol% of the total amount of epoxy monomers and zwitterionic monomers, then placing a reaction system into a three-neck flask, reacting for 6 hours at 90 ℃, after the reaction is finished, dripping a crude product solution into absolute ethyl alcohol to obtain a precipitate, dissolving the precipitate in water, and freeze-drying to obtain white solid powder of an epoxy-zwitterionic copolymer, wherein the epoxy-zwitterionic copolymer is poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-glycidyl methacrylate);
(4) Placing the amino-containing polyvinylidene fluoride ultrafiltration membrane into 20mg/mL poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-allyl alcohol glycidyl ether) solution, then adding 100 mu L ammonium bromide solution into each milliliter of poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-allyl alcohol glycidyl ether) solution, reacting for 24 hours at the temperature of 60 ℃, taking out the membrane after the reaction is finished, washing with ultrapure water for three times, and naturally airing to obtain the anti-pollution polyvinylidene fluoride ultrafiltration membrane.
Example 6
(1) Placing polyvinyl chloride powder in 12wt% tetraethylenepentamine aqueous solution for heat treatment for 24h at 90 ℃, taking out the powder after amination reaction is finished, sequentially cleaning with absolute ethyl alcohol and ultrapure water for three times, and naturally drying to obtain aminated modified polyvinyl chloride powder;
(2) Putting the aminated modified polyvinyl chloride powder into N-methyl pyrrolidone, stirring and dissolving to obtain a casting solution with the concentration of 15wt%, standing, defoaming, carrying out curtain coating and blade coating on the casting solution on a polypropylene non-woven fabric supporting layer by using a scraper, then quickly transferring to ethanol with the temperature of 30 ℃ for curing and forming to obtain a wet film, soaking and cleaning the wet film in ultrapure water, and naturally airing to obtain an amino-containing polyvinyl chloride ultrafiltration membrane;
(3) Preparing a mixed solution of allyl alcohol glycidyl ether and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide (the content of the allyl alcohol glycidyl ether is 60 mol%), stirring uniformly, purging with nitrogen, then adding azodiisovaleronitrile accounting for 8mol% of the total amount of epoxy monomers and zwitterionic monomers, then placing a reaction system into a three-neck flask, reacting for 6 hours at 80 ℃, dropping a crude product solution into absolute ethyl alcohol after the reaction is finished to obtain a precipitate, dissolving the precipitate in water, and freeze-drying to obtain white solid powder of an epoxy-zwitterionic copolymer, wherein the epoxy-zwitterionic copolymer is poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-allyl alcohol) glycidyl ether);
(4) And (2) placing the amino-containing polyvinyl chloride ultrafiltration membrane into 25mg/mL poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-allyl alcohol glycidyl ether) solution, then adding 100 mu L dodecyl trimethyl ammonium chloride solution into each milliliter of poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-allyl alcohol glycidyl ether) solution, reacting at 90 ℃ for 10 hours, taking out the membrane after the reaction is finished, washing with ultrapure water for three times, and naturally drying to obtain the anti-pollution polyvinyl chloride ultrafiltration membrane.
Example 7
(1) Putting the polyimide powder into 5wt% of polyethylene imine water solution, performing heat treatment for 48h at the temperature of 80 ℃, taking out the powder after amination reaction is finished, sequentially cleaning the powder with absolute ethyl alcohol and ultrapure water for three times, and naturally airing to obtain amination modified polyimide powder;
(2) Placing the amination modified polyimide powder into N-methyl pyrrolidone to be stirred and dissolved to obtain a casting solution with the concentration of 10wt%, carrying out standing deaeration, carrying out curtain coating and blade coating on the casting solution on a polypropylene non-woven fabric supporting layer by using a scraper, then quickly transferring the casting solution into 50 ℃ ultra-pure water to be cured and formed to obtain a wet film, placing the wet film into the ultra-pure water to be soaked, cleaned and naturally dried to obtain the amino-containing polyimide ultrafiltration membrane;
(3) Preparing a mixed solution of 4-hydroxybutyl acrylate glycidyl ether and 2-methacryloyloxyethyl phosphorylcholine (the content of the 4-hydroxybutyl acrylate glycidyl ether is 70 mol%), stirring uniformly, purging with nitrogen, adding azodiisoheptonitrile accounting for 7mol% of the total amount of an epoxy monomer and a zwitterionic monomer, placing a reaction system in a three-neck flask, reacting for 10 hours at 90 ℃, dropping a crude product solution into absolute ethyl alcohol after the reaction is finished to obtain a precipitate, dissolving the precipitate in water, and freeze-drying to obtain solid epoxy-zwitterionic copolymer powder, wherein the epoxy-zwitterionic copolymer is poly (2-methacryloyloxyethyl phosphorylcholine-co-4-hydroxybutyl acrylate glycidyl ether);
(4) Putting the amino-containing polyimide ultrafiltration membrane into 30mg/mL poly (2-methacryloyloxyethyl phosphorylcholine-co-4-hydroxybutyl acrylate glycidyl ether) solution, then adding 100 mu L pyridine solution into each mL poly (2-methacryloyloxyethyl phosphorylcholine-co-4-hydroxybutyl acrylate glycidyl ether) solution, reacting for 24h at 50 ℃, taking out the membrane after the reaction is finished, washing with ultrapure water for three times, and naturally airing to obtain the anti-pollution polyimide ultrafiltration membrane.
Example 8
(1) Placing the polyether sulfone powder in 20wt% of diethylenetriamine aqueous solution, carrying out heat treatment for 20h at 170 ℃, taking out the powder after the amination reaction is finished, sequentially cleaning the powder with absolute ethyl alcohol and ultrapure water for three times, and naturally airing to obtain aminated modified polyether sulfone powder;
(2) Placing the aminated modified polyether sulfone powder in acetone, stirring and dissolving to obtain a casting solution with the concentration of 25wt%, standing, defoaming, casting and blade-coating the casting solution on a polypropylene non-woven fabric supporting layer by using a scraper, then quickly transferring to 30 ℃ ultrapure water, curing and forming to obtain a wet film, placing the wet film in the ultrapure water, soaking and cleaning, and naturally airing to obtain an amino-containing polyether sulfone ultrafiltration membrane;
(3) Preparing a mixed solution of glycidyl methacrylate and 2-methacryloyloxyethyl phosphorylcholine (the content of glycidyl methacrylate is 90 mol%), stirring uniformly, purging with nitrogen, adding dibenzoyl peroxide accounting for 3mol% of the total amount of an epoxy monomer and a zwitterionic monomer, placing a reaction system in a three-neck flask, reacting for 3 hours at 90 ℃, dropping a crude product solution into absolute ethyl alcohol after the reaction is finished to obtain a precipitate, dissolving the precipitate in water, and freeze-drying to obtain white solid powder of an epoxy-zwitterionic copolymer, wherein the epoxy-zwitterionic copolymer is poly (2-methacryloyloxyethyl phosphorylcholine-co-glycidyl methacrylate);
(4) Placing the amino-containing polyethersulfone ultrafiltration membrane into 5mg/mL poly (2-methacryloyloxyethyl phosphorylcholine-co-glycidyl methacrylate) solution, then adding 100 microliter triethylamine into each milliliter of poly (2-methacryloyloxyethyl phosphorylcholine-co-glycidyl methacrylate) solution, reacting for 6 hours at 90 ℃, taking out the membrane after the reaction is finished, washing with ultrapure water for three times, and naturally airing to obtain the anti-pollution polyethersulfone ultrafiltration membrane.
Comparative example 1
Compared with the preparation method of the anti-pollution ultrafiltration membrane in the embodiment 1, the preparation method of the anti-pollution ultrafiltration membrane only differs from the preparation method of the anti-pollution ultrafiltration membrane in the embodiment 1: and (5) preparing the amino polyether sulfone-containing ultrafiltration membrane without performing the step (3) and the step (4).
Sample analysis
(1) Morphological and elemental analysis
XPS test results of the amine-containing polyethersulfone ultrafiltration membrane of comparative example 1 and the anti-fouling polyethersulfone ultrafiltration membrane of example 3 were shown as a and B, respectively, in fig. 1, by grafting poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-glycidyl methacrylate) onto the amine-containing polyethersulfone ultrafiltration membrane, a new N element peak was observed on the anti-fouling polyethersulfone ultrafiltration membrane, corresponding to the ammonium ion group in the zwitterion, demonstrating successful grafting of the epoxy-zwitterion copolymer.
(2) Hydrophilic property of anti-pollution ultrafiltration membrane
A certain area of the anti-pollution polyethersulfone ultrafiltration membrane in example 3 and the amino polyethersulfone ultrafiltration membrane in comparative example 1 are respectively cut out and placed on a static water contact angle instrument, and the water contact angle is measured. As shown in FIG. 2, compared with the ultrafiltration membrane containing amino polyether sulfone, the anti-pollution polyether sulfone ultrafiltration membrane has greatly reduced water contact angle, excellent hydrophilicity and a water contact angle of 33 degrees.
(3) Protein pollution resistance of anti-pollution ultrafiltration membrane
The membranes of the examples and the comparative examples, which were cut to a certain area, were placed in a cross-flow flat membrane performance evaluation device, and the pure water flux recovery rate of the membranes was finally measured by filtering the flux change of 1g/L BSA solution (cycle content: pure water 30 min-BSA solution 60 min-washing 30 min-pure water 30 min) under an operating pressure of 0.05 MPa.
As shown in fig. 3, the anti-fouling polyethersulfone ultrafiltration membrane in example 3 exhibited a higher flux recovery rate and had a good anti-protein fouling ability, compared to the amino-containing polyethersulfone ultrafiltration membrane in comparative example 1.
The results of pure water flux recovery of the ultrafiltration membranes of examples 1 to 8 and comparative example 1 are shown in table 1, and it can be seen that the grafting of the epoxy-zwitterionic copolymer on the surface of the amino-containing ultrafiltration membrane significantly improvedThe protein pollution resistance of the membrane is maintained at 140L/m under the condition of operating pressure of 0.05MPa 2 h is about.
TABLE 1 pure water flux recovery results for membranes in examples and comparative examples
| Sample(s) | Pure water flux L/m 2 h | Recovery rate of pure water flux |
| Example 1 | 138 | 94％ |
| Example 2 | 137 | 93％ |
| Example 3 | 140 | 98％ |
| Example 4 | 136 | 96％ |
| Example 5 | 138 | 94％ |
| Example 6 | 139 | 95％ |
| Example 7 | 136 | 97％ |
| Example 8 | 137 | 98％ |
| Comparative example 1 | 120 | 35％ |
(4) Antibacterial adhesion performance of anti-pollution ultrafiltration membrane
A certain area of the anti-pollution polyethersulfone ultrafiltration membrane in the example 3 and the amino polyethersulfone ultrafiltration membrane in the comparative example 1 are respectively cut and placed in a 12-hole plate, and Escherichia coli bacterial suspension is added. Then placing the membrane into a constant-temperature shaking incubator to incubate for a certain time at 37 ℃, taking out the membrane after incubation is finished, washing the membrane with PBS buffer solution for three times, then placing the membrane into glutaraldehyde solution to fix the membrane overnight, taking out the membrane, washing, dehydrating with ethanol with a series of concentration gradients, fully drying, and then shooting SEM images of the surface of the membrane, wherein the result is shown in figure 4, A is the amino polyether sulfone-containing ultrafiltration membrane of the comparative example 1, and B is the anti-pollution polyether sulfone ultrafiltration membrane of the example 3; a large amount of escherichia coli are adhered to the surface of the ultrafiltration membrane containing the amino polyether sulfone, and almost no escherichia coli is adhered to the surface of the anti-pollution polyether sulfone ultrafiltration membrane, so that the anti-pollution ultrafiltration membrane has good antibacterial adhesion capability.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the anti-pollution ultrafiltration membrane is characterized by comprising the following steps:
(1) Carrying out amination modification on the polymer powder to obtain amination modified polymer powder;
(2) Preparing a membrane casting solution by using the aminated modified polymer powder in the step (1), casting the membrane casting solution on a support layer to form a membrane, transferring the membrane casting solution to a coagulating bath to be cured and formed to obtain a wet membrane, and further washing and airing to obtain an amino-containing ultrafiltration membrane;
(3) Taking an epoxy monomer, a zwitterionic monomer and an initiator as raw materials to carry out polymerization reaction to prepare an epoxy-zwitterionic copolymer;
(4) And (3) grafting the epoxy-zwitterionic copolymer to the amino-containing ultrafiltration membrane obtained in the step (2) through an epoxy ring-opening reaction to obtain the anti-pollution ultrafiltration membrane.
2. The method for preparing the anti-pollution ultrafiltration membrane according to claim 1, wherein in the step (1), the polymer powder is placed in an aqueous solution of an amino monomer for amination modification; the amino monomer is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine.
3. The method for preparing the anti-pollution ultrafiltration membrane according to claim 2, wherein the concentration of the aqueous solution of the amino monomer is 5-20wt%; the temperature of amination modification is 80-180 ℃, and the time is 20-70h.
4. The method of claim 1, wherein in step (3), the epoxy monomer is at least one of glycidyl methacrylate, 4-hydroxybutylacrylate glycidyl ether and allyl alcohol glycidyl ether; the zwitterionic monomer is at least one of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate and 2-methacryloyloxyethyl phosphorylcholine.
5. The method for preparing the anti-pollution ultrafiltration membrane according to claim 1, wherein in the step (3), the molar ratio of the epoxy monomer to the zwitterionic monomer is 1:9-9:1, the amount of the initiator is 1-8mol% of the total amount of the epoxy monomer and the zwitterion monomer.
6. The method for preparing the anti-pollution ultrafiltration membrane according to claim 1, wherein the polymerization reaction time in the step (3) is 3-10h and the temperature is 50-90 ℃.
7. The method for preparing the anti-pollution ultrafiltration membrane according to claim 1, wherein in the step (4), the epoxy ring-opening reaction comprises the following specific steps: and (2) placing the amino-containing ultrafiltration membrane in an epoxy-zwitterionic copolymer solution for grafting reaction, wherein the grafting reaction temperature is 50-90 ℃, and the grafting reaction time is 6-24h.
8. The method of claim 7, wherein the concentration of the epoxy-zwitterionic copolymer solution is 5-30mg/mL.
9. The anti-pollution ultrafiltration membrane prepared by the method for preparing the anti-pollution ultrafiltration membrane according to any one of claims 1 to 8.
10. The use of the anti-fouling ultrafiltration membrane of claim 9 in the field of membrane separation.
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