CN115569536B - 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, 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 casting solution by using amination modified polymer powder, casting the casting solution on a supporting layer to form a film, transferring the film to a coagulating bath to be solidified and molded to obtain a wet film, and further washing and airing to obtain an amino-containing ultrafiltration film; (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 onto the amino-containing ultrafiltration membrane in the step (2) through 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 bacterial 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 and 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 filtering process, easy control and the like, and becomes one of the most potential technologies in the fields of water treatment, hemodialysis and the like. The membrane can be divided into microfiltration membrane, ultrafiltration membrane, nanofiltration membrane, reverse osmosis membrane, etc. from application process, wherein the minimum molecular weight cut-off of ultrafiltration membrane is 2000 daltons, and can be used for separating protein, enzyme, nucleic acid, polysaccharide, polypeptide, antibiotic, virus, etc. The ultrafiltration membrane has no phase transfer in the use process, no toxic or harmful chemical substances are required to be added, and the application is wide.
In the use process of the ultrafiltration membrane, the deposition or adsorption of various pollutants can cause serious decline 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 a contaminant source, membrane pollution mainly includes inorganic pollution, organic pollution and biological pollution. Among them, biological pollution is a common problem faced by ultrafiltration membranes in the fields of water treatment and hemodialysis, and inhibition of protein pollution and bacterial adhesion is an important way to control biological pollution. In order to solve the pollution problem in the use process of the ultrafiltration membrane, the common methods mainly comprise raw material treatment, membrane separation process optimization, membrane cleaning, membrane anti-pollution development and the like, wherein the first three methods all need to introduce other operations, increase the cost, can not radically treat the membrane pollution, and the membrane anti-pollution development is used for inhibiting the interaction of a pollution source and a membrane material, so that the method is a fundamental method for solving the membrane pollution.
The Chinese patent document with publication number of CN112316754A discloses a preparation method of an anti-pollution hollow fiber ultrafiltration membrane: adding magnetic nano particles into the casting solution by adopting a blending method, and then spinning to prepare the anti-pollution hollow fiber ultrafiltration membrane, wherein the weight percentage of the magnetic nano particles in the casting solution is 0.1% -5%; the hollow fiber ultrafiltration membrane prepared by the method has magnetism, can swing under the action of a magnetic field, is favorable for cleaning pollutants from the surface and the hollow interior of the membrane wire, but the magnetic nano particles blended and doped by the method have the risk of falling off in the preparation and use processes of the membrane, can cause secondary pollution and is not suitable for long-term use.
The Chinese patent document with publication number of CN108579438A discloses a preparation method of a high-flux anti-pollution polyvinyl chloride ultrafiltration membrane, which comprises the steps of mixing a polymer with an organic solvent, heating and activating the mixture under the protection of nitrogen, adding an amphiphilic block copolymer, continuously stirring the mixture to completely dissolve the polymer and the amphiphilic block copolymer, and finally standing and defoaming the mixture to obtain a casting membrane solution; dissolving inorganic salt in deionized water to obtain a coagulation bath; pouring the casting solution onto a glass plate, scraping the glass plate with the casting solution by using a scraper, immersing the glass plate with the casting solution into a coagulating bath, and taking out the glass plate after gelation to obtain the high-flux anti-pollution polyvinyl chloride ultrafiltration membrane. According to the method, anti-pollution substances are introduced in the stirring process, so that the anti-pollution substances are very easy to wrap in the film making 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 and mild reaction condition, and the prepared anti-pollution ultrafiltration membrane has good hydrophilicity, excellent protein pollution resistance and antibacterial adhesion resistance, and can maintain higher pure water flux.
The technical scheme adopted is as follows:
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 casting solution by using the amination modified polymer powder in the step (1), casting the casting solution on a supporting layer to form a film, transferring the film to a coagulating bath to be solidified and molded to obtain a wet film, and washing and airing the wet film to obtain the ultrafiltration film containing amino groups;
(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 onto the amino-containing ultrafiltration membrane in the step (2) through epoxy ring-opening reaction to obtain the anti-pollution ultrafiltration membrane.
The invention aminates polymer powder, and prepares an amino-containing ultrafiltration membrane by utilizing the phase conversion of an aminated polymer solution; then, utilizing the amino group on the amino-containing ultrafiltration membrane and the epoxy-zwitterionic copolymer to carry out epoxy ring-opening reaction, thereby grafting the zwitterionic polymer on the amino-containing ultrafiltration membrane to prepare the anti-pollution ultrafiltration membrane; the epoxy-zwitterionic copolymer is connected with the amino-containing ultrafiltration membrane through a covalent bond, the binding force is strong, and the grafted zwitterionic polymer is provided with positive and negative groups at the same time, so that a hydration layer is easy to form, and the hydration effect is strong, thereby having the capability of resisting protein pollution. The method has low equipment requirement, simple preparation method, convenient improvement on the basis of the traditional ultrafiltration membrane preparation process, realization of amplified production, good hydrophilicity of the obtained anti-pollution ultrafiltration membrane, excellent protein pollution resistance, high pure water flux maintenance, good antibacterial adhesion capability, and wide prospect 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 step (1), the polymer powder is placed in an aqueous amino monomer solution for amination modification; the amino monomer is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, 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.
According to the invention, the polymer powder is subjected to amination modification, and then the amination modified polymer powder is utilized to prepare the membrane, so that the amination modification degree is high, parameters such as the thickness, the pore diameter and the like of the membrane are easy to adjust, and the membrane preparation parameters can be adjusted according to the requirements of products.
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 coagulating bath is water, methanol or ethanol, and the coagulating bath temperature is 20-50 ℃.
The synthesis and grafting of the epoxy-zwitterionic copolymer are key to the preparation of 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 initiator is 1-8mol% of the total amount of the epoxy monomer and the zwitterionic 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 and react for 3-10 hours under the condition of heating and stirring at 50-90 ℃ 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 subjected to freeze drying to obtain the epoxy-zwitterionic copolymer.
The structural formula of the epoxy-zwitterionic copolymer is expressed as follows:
wherein R is 1 R is the residue of said zwitterionic monomer 2 And m and n are positive integers from 1 to 100 for the epoxy monomer residue.
Preferably, the number average molecular weight of the epoxy-zwitterionic copolymer is 20000-30000.
Preferably, in the step (4), the specific steps of the epoxy ring-opening reaction are as follows: and (3) placing the ultrafiltration membrane containing amino groups 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.
Further preferably, the concentration of the epoxy-zwitterionic copolymer solution is 5-30mg/mL; the product film produced in the above preferred concentration range is excellent in hydrophilicity.
The catalyst for 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 an 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 antibacterial adhesion resistance, can maintain higher pure water flux, and can be applied to aspects of water treatment, hemodialysis and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) Under the action of an initiator, the epoxy monomer and the zwitterionic monomer are subjected to free radical polymerization to synthesize the epoxy-zwitterionic copolymer, the zwitterionic is anchored on the amino-containing ultrafiltration membrane through an epoxy ring-opening reaction, the epoxy-zwitterionic copolymer is connected with the amino-containing ultrafiltration membrane through a covalent bond, the binding force is strong, and the constructed modified layer is more stable than non-covalent modification methods such as surface coating, blending doping and the like, so that 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 the amination modified polymer powder, the raw material polymer powder is modified, and the whole process of preparing the ultrafiltration membrane by using the phase inversion method is optimized, so that grafting sites of an 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-zwitterionic copolymer is grafted onto the amino-containing ultrafiltration membrane, and the prepared anti-pollution ultrafiltration membrane has good protein pollution resistance and antibacterial adhesion resistance, has good hydrophilicity, has a water contact angle of at least 33 degrees, and can maintain higher pure water flux.
(4) The preparation method of the anti-pollution ultrafiltration membrane provided by the invention is simple, has low equipment requirement, is easy to store, has long service life, low preparation cost and no toxic and harmful substance residue, is convenient to realize amplified preparation and production, and has wide prospects in the fields of water treatment and hemodialysis.
Drawings
FIG. 1 is a graph showing XPS analysis results of the anti-fouling 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-fouling polyethersulfone membrane of example 3.
FIG. 2 is a graph showing the water contact angle between the anti-fouling ultrafiltration membrane of example 3 and the amino-containing ultrafiltration membrane of comparative example 1.
FIG. 3 is a graph showing the flux-time change of the anti-fouling ultrafiltration membrane of example 3 and the amino-containing ultrafiltration membrane of comparative example 1 for filtering 1g/L bovine serum albumin solution.
FIG. 4 is an E.coli adhesion scanning electron microscope image of the anti-fouling 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-fouling polyethersulfone membrane of example 3.
Detailed Description
The invention is further illustrated by the following examples. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
Zwitterionic monomers 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate (CAS number 24249-95-4), 2-methacryloyloxyethyl phosphorylcholine (CAS: 67881-98-5), and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide (CAS: 3637-26-1) were purchased from Shanghai source leaf Biotechnology Co.
Example 1
(1) Placing polysulfone powder into 5wt% ethylenediamine water solution, heat treating at 80deg.C for 70h, taking out the powder after amination reaction, sequentially cleaning with absolute ethanol and ultrapure water for three times, and naturally air-drying to obtain aminated modified polysulfone powder;
(2) Placing the amination modified polysulfone powder into acetone for stirring and dissolving to obtain casting solution with the concentration of 15wt%, standing and defoaming, then using a scraper to carry out casting solution casting and knife coating on a polypropylene non-woven fabric supporting layer, then rapidly transferring into 20 ℃ ultrapure water for curing and forming to obtain a wet membrane, soaking and cleaning the wet membrane in the ultrapure water, and naturally airing to obtain the polysulfone ultrafiltration membrane containing amino groups;
(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 10mol percent), stirring uniformly, then purging with nitrogen, adding azobisisobutyronitrile accounting for 1mol percent of the total amount of epoxy monomers and zwitterionic monomers, then placing the reaction system in a three-neck flask, reacting for 10 hours at 50 ℃, dripping the 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-4-hydroxybutyl acrylate glycidyl ether);
(4) The polysulfone ultrafiltration membrane containing amino groups is placed in 5mg/mL poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-4-hydroxybutyl acrylate glycidyl ether) solution, then 100 mu L of pyridine solution is added per milliliter of poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-4-hydroxybutyl acrylate glycidyl ether) solution, the reaction is carried out for 24 hours at 50 ℃, after the reaction is finished, the membrane is taken out, the ultra-pure water is washed for three times, and the anti-pollution polysulfone ultrafiltration membrane is obtained after natural airing.
Example 2
(1) Placing polyether sulfone powder into 8wt% of hexamethylenediamine water solution, performing heat treatment at 100 ℃ for 60 hours, 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 amination modified polyethersulfone powder into N, N-dimethylformamide to be stirred and dissolved to obtain casting solution with the concentration of 17wt%, standing and defoaming, then spreading the casting solution on a polypropylene non-woven fabric supporting layer by using a scraper, rapidly transferring the casting solution into 25 ℃ ultrapure water to be cured and molded to obtain a wet film, soaking and cleaning the wet film in the ultrapure water, and naturally airing the wet film to obtain the ultrafiltration membrane containing the amino polyethersulfone;
(3) Preparing a mixed solution of glycidyl methacrylate and 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate (the content of the glycidyl methacrylate is 10mol percent), stirring uniformly, purging with nitrogen, then adding azodiisovaleronitrile accounting for 3mol percent of the total amount of epoxy monomers and zwitterionic monomers, placing a reaction system in a three-neck flask, reacting for 4 hours at 70 ℃, dripping the 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 epoxy-zwitterionic copolymer white solid powder, wherein the epoxy-zwitterionic copolymer is poly (3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate-co-glycidyl methacrylate);
(4) The ammonia-containing polyethersulfone ultrafiltration membrane is placed in 7mg/mL poly (3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate-co-methacrylic acid glycidyl ester) solution, then 100 mu L of dodecyl trimethyl ammonium chloride solution is added per milliliter of poly (3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate-co-methacrylic acid glycidyl ester) solution, the reaction is carried out for 6 hours at 50 ℃, after the reaction is finished, the membrane is taken out, ultrapure water is washed for three times, and the anti-pollution polyethersulfone ultrafiltration membrane is obtained after natural airing.
Example 3
(1) Placing polyethersulfone powder into 10wt% diethylenetriamine water solution, heat treating for 70 hours at 80 ℃, 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 amination modified polyethersulfone powder;
(2) Placing the amination modified polyethersulfone powder into N, N-dimethylformamide to be stirred and dissolved to obtain casting solution with the concentration of 20wt%, standing and defoaming, then spreading the casting solution on a polypropylene non-woven fabric supporting layer by using a scraper, rapidly transferring the casting solution into 50 ℃ ultrapure water to be cured and molded to obtain a wet film, soaking and cleaning the wet film in the ultrapure water, and naturally airing the wet film to obtain the ultrafiltration membrane containing the amino polyethersulfone;
(3) Preparing a mixed solution of glycidyl methacrylate and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide (the content of the glycidyl methacrylate is 20mol percent), stirring uniformly, then purging with nitrogen, adding azobisisobutyronitrile accounting for 1mol percent of the total amount of epoxy monomers and zwitterionic monomers, then placing the reaction system in a three-neck flask, reacting for 6 hours at 70 ℃, dripping the 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 epoxy-zwitterionic copolymer white solid powder, 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 specification, wherein x and y are positive integers of 1-100.
(4) The ultrafiltration membrane containing amino polyethersulfone is placed in 30mg/mL poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-glycidyl methacrylate) solution, then 100 mu L of triethylamine solution is added per milliliter of poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-glycidyl methacrylate) solution, the reaction is carried out for 12 hours at 60 ℃, after the reaction is finished, the membrane is taken out, the ultra-pure water is washed three times, and the anti-pollution polyethersulfone ultrafiltration membrane is obtained after natural airing.
Example 4
(1) Placing polyacrylonitrile powder into a triethylene tetramine water solution with the weight percentage of 20 to be subjected to heat treatment for 30 hours at the temperature of 180 ℃, 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 polyacrylonitrile powder;
(2) Placing the amination modified polyacrylonitrile powder into tetrahydrofuran, stirring and dissolving to obtain casting solution with the concentration of 25wt%, standing and defoaming, then using a scraper to carry out casting solution casting and knife coating on a polypropylene non-woven fabric supporting layer, then rapidly transferring into 40 ℃ methanol for curing and forming to obtain a wet film, soaking and cleaning the wet film in ultrapure water, and naturally airing to obtain the ultrafiltration membrane containing the amino polyacrylonitrile;
(3) Preparing a mixed solution of allyl alcohol glycidyl ether and 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate (the content of the allyl alcohol glycidyl ether is 30mol percent), stirring uniformly, then purging with nitrogen, adding dibenzoyl peroxide accounting for 3mol percent of the total amount of epoxy monomers and zwitterionic monomers, then placing a reaction system in a three-neck flask, reacting for 6 hours at the temperature of 80 ℃, dripping the 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 epoxy-zwitterionic copolymer white solid powder, wherein the epoxy-zwitterionic copolymer is poly (3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate-co-allyl alcohol glycidyl ether);
(4) The ammonia-containing polyacrylonitrile ultrafiltration membrane is placed in 20mg/mL poly (3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate-co-allyl alcohol glycidyl ether) solution, then 100 mu L of sodium hydroxide solution is added per milliliter of poly (3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate-co-allyl alcohol glycidyl ether) solution, the reaction is carried out for 20 hours at 80 ℃, after the reaction is finished, the membrane is taken out, the ultra-pure water is washed three times, and the anti-pollution polyacrylonitrile ultrafiltration membrane is obtained after natural airing.
Example 5
(1) Placing polyvinylidene fluoride powder into 15wt% tetraethylenepentamine water solution, performing heat treatment for 50 hours at 100 ℃, 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 polyvinylidene fluoride powder;
(2) Placing 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 spreading the casting solution on a polypropylene non-woven fabric supporting layer by using a doctor blade, rapidly transferring into 40 ℃ methanol 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 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 40mol percent), stirring uniformly, then purging with nitrogen, then adding azodiisoheptanenitrile accounting for 3mol percent of the total amount of epoxy monomers and zwitterionic monomers, then placing the reaction system in a three-neck flask, reacting for 6 hours under the reaction condition of 90 ℃, dripping the 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-glycidyl methacrylate);
(4) The amino-containing polyvinylidene fluoride ultrafiltration membrane is placed in 20mg/mL poly (2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-allyl alcohol glycidyl ether) solution, then 100 mu L of ammonium bromide solution is added per milliliter of poly (2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-allyl alcohol glycidyl ether) solution, the reaction is carried out for 24 hours at 60 ℃, after the reaction is finished, the membrane is taken out, the ultra-pure water is washed three times, and the anti-pollution polyvinylidene fluoride ultrafiltration membrane is obtained after natural airing.
Example 6
(1) Placing polyvinyl chloride powder into 12wt% tetraethylenepentamine water solution, heat treating for 24 hours at 90 ℃, 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 amination modified polyvinyl chloride powder;
(2) Placing the amination modified polyvinyl chloride powder into N-methyl pyrrolidone for stirring and dissolving to obtain a casting solution with the concentration of 15wt%, standing and defoaming, then using a scraper to carry out casting solution casting and knife coating on a polypropylene non-woven fabric supporting layer, then rapidly transferring the polypropylene non-woven fabric supporting layer into ethanol with the temperature of 30 ℃ for curing and forming to obtain a wet film, placing the wet film into ultrapure water for soaking and cleaning, 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 60mol percent), stirring uniformly, purging with nitrogen, then adding azodiisovaleronitrile accounting for 8mol percent of the total amount of epoxy monomers and zwitterionic monomers, placing a reaction system in a three-neck flask, reacting for 6 hours at the temperature of 80 ℃, dripping the 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 epoxy-zwitterionic copolymer white solid powder, wherein the epoxy-zwitterionic copolymer is poly (2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-allyl alcohol glycidyl ether) white solid powder;
(4) The method comprises the steps of placing an amino-containing polyvinyl chloride ultrafiltration membrane in 25mg/mL of poly (2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-allyl alcohol glycidyl ether) solution, adding 100 mu L of 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 for 10 hours at 90 ℃, taking out a membrane after the reaction is finished, flushing with ultrapure water for three times, and naturally airing to obtain the anti-pollution polyvinyl chloride ultrafiltration membrane.
Example 7
(1) Placing polyimide powder into 5wt% polyethylenimine water solution, heat treating for 48 hours at 80 ℃, 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 amination modified polyimide powder;
(2) Placing the amination modified polyimide powder into N-methyl pyrrolidone for stirring and dissolving to obtain casting solution with the concentration of 10wt%, standing and defoaming, then using a scraper to carry out casting solution casting and knife coating on a polypropylene non-woven fabric supporting layer, then rapidly transferring into 50 ℃ ultrapure water for curing and forming to obtain a wet film, placing the wet film into the ultrapure water for soaking and cleaning, and naturally airing to obtain the amino-containing polyimide ultrafiltration membrane;
(3) Preparing a mixed solution of 4-hydroxybutyl acrylate glycidyl ether and 2-methacryloxyethyl phosphorylcholine (the content of the 4-hydroxybutyl acrylate glycidyl ether is 70mol percent), stirring uniformly, then purging with nitrogen, adding azodiisoheptonitrile accounting for 7mol percent of the total amount of epoxy monomers and zwitterionic monomers, then placing a reaction system in a three-neck flask, reacting for 10 hours at the temperature of 90 ℃, dripping 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 epoxy-zwitterionic copolymer solid powder, wherein the epoxy-zwitterionic copolymer is poly (2-methacryloxyethyl phosphorylcholine-co-4-hydroxybutyl acrylate glycidyl ether);
(4) And (3) placing the amino-containing polyimide ultrafiltration membrane into 30mg/mL of poly (2-methacryloyloxyethyl phosphorylcholine-co-4-hydroxybutyl acrylate glycidyl ether) solution, adding 100 mu L of pyridine solution into each milliliter of poly (2-methacryloyloxyethyl phosphorylcholine-co-4-hydroxybutyl acrylate glycidyl ether) solution, reacting for 24 hours at 50 ℃, taking out the membrane after the reaction is finished, flushing with ultrapure water for three times, and naturally airing to obtain the anti-pollution polyimide ultrafiltration membrane.
Example 8
(1) Placing polyether sulfone powder into a 20wt% diethylenetriamine water solution, performing heat treatment for 20 hours 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 amination modified polyether sulfone powder;
(2) Placing the amination modified polyethersulfone powder into acetone, stirring and dissolving to obtain casting solution with the concentration of 25wt%, standing and defoaming, then using a scraper to carry out casting solution casting and knife coating on a polypropylene non-woven fabric supporting layer, then rapidly transferring into 30 ℃ ultrapure water for curing and forming to obtain a wet film, placing the wet film into the ultrapure water for soaking and cleaning, and naturally airing to obtain the ultrafiltration membrane containing the amino polyethersulfone;
(3) Preparing a mixed solution of glycidyl methacrylate and 2-methacryloxyethyl phosphorylcholine (the content of the glycidyl methacrylate is 90mol percent), stirring uniformly, purging with nitrogen, then adding dibenzoyl peroxide accounting for 3mol percent of the total amount of epoxy monomers and zwitterionic monomers, placing a reaction system in a three-neck flask, reacting for 3 hours at the temperature of 90 ℃, dripping the 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 epoxy-zwitterionic copolymer white solid powder, wherein the epoxy-zwitterionic copolymer is poly (2-methacryloxyethyl phosphorylcholine-co-glycidyl methacrylate);
(4) And (3) placing the amino-containing polyether sulfone ultrafiltration membrane into 5mg/mL of poly (2-methacryloyloxyethyl phosphorylcholine-co-glycidyl methacrylate) solution, adding 100 mu L of triethylamine per milliliter of the poly (2-methacryloyloxyethyl phosphorylcholine-co-glycidyl methacrylate) solution, reacting for 6 hours at 90 ℃, taking out the membrane after the reaction is finished, flushing with ultrapure water for three times, and naturally airing to obtain the anti-pollution polyether sulfone ultrafiltration membrane.
Comparative example 1
Compared with the embodiment 1, the preparation method of the anti-pollution ultrafiltration membrane is only different in that: and (3) and (4) are not carried out, and the ultrafiltration membrane containing the amino polyethersulfone is prepared.
Sample analysis
(1) Morphology and elemental analysis
The XPS test results of the amino polyethersulfone ultrafiltration membrane in comparative example 1 and the anti-fouling polyethersulfone ultrafiltration membrane in example 3 are shown as A and B in FIG. 1, respectively, and successful grafting of the epoxy-zwitterionic copolymer was demonstrated by grafting poly ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide-co-glycidyl methacrylate) onto the amino polyethersulfone ultrafiltration membrane such that the anti-fouling polyethersulfone ultrafiltration membrane exhibited a new N element peak corresponding to the ammonium ion groups in the zwitterions.
(2) Hydrophilic properties of anti-pollution ultrafiltration membranes
The anti-pollution polyethersulfone ultrafiltration membrane in example 3 and the amino-containing polyethersulfone ultrafiltration membrane in comparative example 1, which are respectively cut into a certain area, are placed on a static water contact angle meter, and the water contact angle is measured. As shown in figure 2, the anti-pollution polyethersulfone ultrafiltration membrane has the advantages of greatly reduced water contact angle, excellent hydrophilicity and water contact angle of 33 degrees compared with the ultrafiltration membrane containing amino polyethersulfone.
(3) Protein contamination resistance of an anti-contamination ultrafiltration membrane
The membranes of the examples and the comparative examples with certain areas were cut out respectively and 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 bovine serum albumin solution (circulation content: pure water 30 min-bovine serum albumin solution 60 min-cleaning 30 min-pure water 30 min) under the condition of an operating pressure of 0.05 MPa.
As shown in fig. 3, the anti-fouling polyethersulfone ultrafiltration membrane of example 3 exhibited a higher flux recovery rate and had a good ability to resist protein contamination as compared to the amino-containing polyethersulfone ultrafiltration membrane of comparative example 1.
The pure water flux recovery rate results of the ultrafiltration membranes of examples 1 to 8 and comparative example 1 are shown in Table 1, and it can be seen that grafting of the epoxy-zwitterionic copolymer on the surface of the amino-containing ultrafiltration membrane significantly improves the protein contamination resistance of the membrane, and the flux is maintained at 140L/m under the operating pressure of 0.05MPa 2 h is about.
Table 1 pure water flux recovery rate results for membranes in examples and comparative examples
| Sample of | Pure water flux L/m 2 h | Pure water flux recovery rate |
| 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
The anti-pollution polyethersulfone ultrafiltration membrane in the example 3 and the amino-containing polyethersulfone ultrafiltration membrane in the comparative example 1, which are respectively cut into a certain area, are placed in a 12-hole plate, and the escherichia coli bacterial suspension is added. Then placing the membrane in a constant temperature shaking incubator at 37 ℃ for incubation for a certain time, taking out the membrane after incubation, washing the membrane with PBS buffer solution for three times, then placing the membrane in glutaraldehyde solution for fixing overnight, taking out the membrane, washing the membrane, dehydrating the membrane by serial concentration gradient ethanol, and fully drying the membrane, and shooting SEM images of the surface of the membrane, wherein A is an amino-containing polyethersulfone ultrafiltration membrane of comparative example 1, and B is an anti-pollution polyethersulfone ultrafiltration membrane of example 3; the surface of the amino-containing polyethersulfone ultrafiltration membrane is adhered with a large amount of escherichia coli, and the surface of the anti-pollution polyethersulfone ultrafiltration membrane is almost free from escherichia coli adhesion, so that the anti-pollution ultrafiltration membrane has good anti-bacterial adhesion capability.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (5)
1. The preparation method of the anti-pollution ultrafiltration membrane is characterized by comprising the following steps of:
(1) Carrying out amination modification on the polymer powder to obtain amination modified polymer powder;
(2) Preparing a casting solution by using the amination modified polymer powder in the step (1), casting the casting solution on a supporting layer to form a film, transferring the film to a coagulating bath to be solidified and molded to obtain a wet film, and further washing and airing the wet film to obtain the ultrafiltration film containing amino groups;
(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) Grafting the epoxy-zwitterionic copolymer onto the amino-containing ultrafiltration membrane in the step (2) through epoxy ring-opening reaction to obtain the anti-pollution ultrafiltration membrane;
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;
in the step (3), the molar ratio of the epoxy monomer to the zwitterionic monomer is 1:9-9:1, the initiator is used in an amount of 1-8mol% of the total amount of the epoxy monomer and the zwitterionic monomer;
in the step (3), the polymerization reaction time is 3-10h, and the temperature is 50-90 ℃;
in the step (4), the specific steps of the epoxy ring-opening reaction are as follows: placing the ultrafiltration membrane containing amino group into an epoxy-zwitterionic copolymer solution for grafting reaction, wherein the grafting reaction temperature is 50-90 ℃ and the grafting reaction time is 6-24 h;
the concentration of the epoxy-zwitterionic copolymer solution is 5-30 mg/mL.
2. The method for producing an anti-fouling ultrafiltration membrane according to claim 1, wherein in the step (1), the polymer powder is placed in an aqueous amino monomer solution for amination modification; the amino monomer is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine.
3. The method for producing an anti-fouling ultrafiltration membrane according to claim 2, wherein 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.
4. An anti-fouling ultrafiltration membrane prepared by the method for preparing an anti-fouling ultrafiltration membrane according to any one of claims 1 to 3.
5. The use of an anti-fouling ultrafiltration membrane according to claim 4 in the field of membrane separation.
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