CN111318172B - Preparation method of polymer-modified graphene filtering membrane - Google Patents
Preparation method of polymer-modified graphene filtering membrane Download PDFInfo
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- CN111318172B CN111318172B CN201811544413.0A CN201811544413A CN111318172B CN 111318172 B CN111318172 B CN 111318172B CN 201811544413 A CN201811544413 A CN 201811544413A CN 111318172 B CN111318172 B CN 111318172B
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- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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Abstract
The invention discloses a preparation method of a polymer modified graphene filtering membrane, and belongs to the technical field of oil-water separation membrane materials. The technical scheme comprises the following steps: coating polydopamine on the surface of the stainless steel mesh after cleaning treatment, and then reacting with graphene oxide to prepare a graphene oxide/polydopamine surface-coated stainless steel mesh; and grafting the polymer on a stainless steel mesh coated on the surface of the graphene oxide/polydopamine by using a Michael addition reaction under an alkaline condition to obtain the super-hydrophilic polymer modified graphene filtering membrane. The invention has the beneficial effects that: according to the invention, the special wetting polymer is coated on the stainless steel mesh substrate with higher mechanical strength, and graphene oxide is more firmly locked on the stainless steel mesh coated on the surface of polydopamine, so that the prepared super-hydrophilic oil-water separation membrane has good mechanical property and long service life; the preparation method is simple and easy to implement, low in cost and wide in application prospect.
Description
Technical Field
The invention relates to the technical field of oil-water separation membrane materials, in particular to a preparation method of a high-molecular modified graphene filtering membrane.
Background
With the rapid development of the industry in China, the discharge amount of oily wastewater is increased year by year, and the components are increasingly complex. If the oil field wastewater is directly discharged without being treated, not only the great waste of water resources is caused, but also the serious environmental pollution is caused. With the improvement of national environmental protection requirements and the proposal of energy-saving and emission-reducing policies, the oily wastewater treatment technology becomes an important factor influencing the sustainable development of oil fields.
The membrane separation technology is a novel oil-water separation mode, and has the advantages of low energy consumption, high single-stage separation efficiency, flexible and simple process, low environmental pollution, strong universality and the like. Membranes are the core of membrane separation technology. With the development of material science, the research and development of surface materials based on special wettability are rapid in recent years, and the surface materials mainly comprise super-hydrophilic, super-hydrophobic, super-oleophilic, super-oleophobic, super-amphiphobic, super-amphiphilic surfaces and the like. The super-oleophobic or super-hydrophobic separation material is obtained by designing the special wettability of the surface of the material, which is undoubtedly the most effective means for improving the oil-water separation performance, especially a membrane with super-hydrophilic and underwater super-oleophobic performances.
The three-dimensional porous graphene assembly is used as a membrane material, the large-scale low-cost preparation of the graphene nano material is realized in the prior art, and the three-dimensional porous graphene assembly prepared by using the graphene nano material as a raw material is low in cost, simple in preparation process, high in mechanical strength and high in chemical and thermal stability, and can be further popularized and applied as an excellent membrane material. The intelligent temperature-sensitive polymer is further modified on the surface of the graphene assembly, so that the graphene composite filtering membrane with excellent super-hydrophilicity and underwater super-lipophobicity at normal temperature can be prepared, and the graphene composite filtering membrane is high in separation efficiency, high in separation speed, environment-friendly, excellent in anti-fouling performance, recyclable and long in service life.
On the basis, in order to achieve the practical field application of the graphene membrane, the graphene membrane is generally required to be fixed on a dead-end filtration device or a cross-flow filtration device for use. In the process, the membrane body is required to bear huge pressure from a liquid column, so that the graphene membrane is required to have certain mechanical strength; therefore, how to coat the wettable polymer material on different substrate materials to improve the strength of the graphene film is a problem which needs to be solved urgently at present.
The application number of 201810568258.X, and the name of 'an oxidized graphene/polydopamine surface-modified oil-water separation steel wire mesh' discloses a oxidized graphene/polydopamine surface-modified stainless steel wire mesh with high-efficiency floating oil separation capacity and a preparation method thereof.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a high-polymer modified graphene filtering membrane with high coating strength.
In order to achieve the above object, the present invention provides a method for preparing a polymer-modified graphene filtration membrane, comprising the following steps:
step (1), coating polydopamine on the surface of the stainless steel net after cleaning treatment;
reacting the stainless steel net coated with the polydopamine on the surface in the step (1) with graphene oxide to obtain a graphene oxide/polydopamine surface-coated stainless steel net;
step (3) adding polymer P (MeO) with sulfhydryl at end through Michael addition reaction under alkaline condition2MA-co-OEGMA-SH) to be grafted on the stainless steel mesh coated on the surface of the graphene oxide/polydopamine prepared in the step (2), so as to prepare the super-hydrophilic polymer modified graphene filtering membrane.
Preferably, the Michael addition reaction in step (3) is carried out in a Bicine buffer solution at a pH of 8.0 to 9.0 and a concentration of 0.05 to 0.15M.
The Bicine buffer solution can be prepared by the following preparation method: 16.317g N, N-dihydroxyethyl glycine is dissolved in 1000mL of deionized water to prepare 0.1M Bicine solution; 2.4g of NaOH is dissolved in 600mL of deionized water to prepare 0.1M NaOH solution; 1000mL of 0.1M Bicine solution and 600mL of 0.1M NaOH solution are mixed to obtain the Bicine buffer solution.
Further preferably, the michael addition reaction in the step (3) is specifically: polymerizing polymer P (MeO)2MA-co-OEGMA-SH) is dissolved in Bicine buffer solution and uniformly mixed, then a stainless steel net coated on the surface of the oxidized graphene/polydopamine is placed in the solution, and the solution is stirred for 18 to 36 hours at room temperature, so that the high-molecular modified graphene filtering membrane can be obtained.
Preferably, the polymer P (MeO) in the step (3)2MA-co-OEGMA-SH) can be prepared by the following preparation method: 2-methyl-2-acrylic acid-2 (2-methoxyethoxy) ethyl ester and oligo-polyethylene glycol methyl ether methacrylate are taken as monomers, and bis [2- (2' -bromo-isobutyryloxy) ethyl]Synthesizing P (MeO) by atom transfer radical polymerization reaction by using disulfide as initiator, cuprous bromide as catalyst and 2, 2' -bipyridine as ligand2MA-co-OEGMA-S-S-MeO2MA-co-OEGMA) copolymer; then tributyl phosphine is used as a reduction catalyst to break disulfide bonds in the polymer to obtain a polymer P (MeO) with a sulfhydryl group at the end2MA-co-OEGMA-SH)。
Further preferably, the oligoethylene glycol methyl ether methacrylate is selected from monomers with a molecular weight of 475g/mol, which are named OEGMA475(ii) a The copolymer synthesized by atom transfer radical polymerization is P (MeO)2MA-co-OEGMA475-S-S- MeO2MA-co-OEGMA475) The copolymer with the mercapto at the end is P (MeO)2MA-co-OEGMA475-SH)。
Further preferably, the feeding molar ratio of the monomer 2-methyl-2-acrylic acid-2 (2 methoxyethoxy) ethyl ester to the oligoethylene glycol methyl ether methacrylate is 5: 1-20:1, initiator bis [2- (2' -bromo isobutyryloxy) ethyl]The using amount of disulfide is 1/150-1/50 of the molar weight of 2- (2 methoxyethoxy) ethyl 2-methyl-2-acrylate monomer, the using amount of cuprous bromide serving as a catalyst is 1/50-1/15 of the molar weight of 2- (2 methoxyethoxy) ethyl 2-methyl-2-acrylate monomer, the using amount of 2, 2' -bipyridyl serving as a ligand is 0.5-3 times of the molar weight of the catalyst, and the using amount of tributylphosphine is P (MeO)2MA-co-OEGMA-S-S-MeO2MA-co-OEGMA) 1/4-1/2, more preferably 1/3.
Even more preferably: the using amount of the initiator bis [2- (2 '-bromoisobutyryloxy) ethyl ] disulfide is 1/100 of the molar amount of the monomer 2-methyl-2 acrylic acid-2 (2 methoxyethoxy) ethyl ester, the using amount of the catalyst cuprous bromide is 1/25 of the molar amount of the monomer 2-methyl-2 acrylic acid-2 (2 methoxyethoxy) ethyl ester, and the using amount of the ligand 2, 2' -bipyridyl is 1.5 times of the molar amount of the catalyst.
Further preferably, the polymer P (MeO)2The preparation method of MA-co-OEGMA-SH) comprises the following steps:
dissolving a monomer 2-methyl-2-acrylic acid-2 (2 methoxyethoxy) ethyl ester and oligoethylene glycol methyl ether methacrylate in anhydrous methanol, sealing, and introducing argon to remove oxygen; initiator bis [2- (2' -bromo isobutyryloxy) ethyl]Disulfide, cuprous bromide as catalyst and 2, 2-bipyridyl-pyridine as ligandAdding into the system again, and continuously introducing argon; then reacting for 6-10h at 45-55 ℃, exposing the reaction solution to air after the reaction is finished, stopping the reaction, adding ethanol for dilution, and removing the copper catalyst through a 60-200 mesh silica column; removing most of methanol and ethanol by rotary evaporation, adding hexane, precipitating polymer, filtering to obtain P (MeO)2MA-co-OEGMA475-S-S-MeO2MA-co-OEGMA475) A polymer; mixing 1g P (MeO)2MA-co-OEGMA475-S-S-MeO2MA-co-OEGMA475) Dissolving in solvent dichloromethane, adding 300-500 μ L tributyl phosphine as reduction catalyst at room temperature, rapidly stirring the mixture for 20-40 min, and removing the solvent by rotary evaporation to obtain monosulfided polymer P (MeO)2MA-co-OEGMA475-SH)。
Even more preferably, the polymer P (MeO)2The preparation method of MA-co-OEGMA-SH) comprises the following steps:
dissolving a monomer 2-methyl-2-acrylic acid-2 (2 methoxyethoxy) ethyl ester and oligoethylene glycol methyl ether methacrylate in anhydrous methanol, placing the mixture in a Schlenk tube, sealing the tube, and introducing argon for 15min to remove oxygen; initiator bis [2- (2' -bromo isobutyryloxy) ethyl]Adding a disulfide, cuprous bromide as a catalyst and 2, 2-bipyridyl as a ligand into the system in sequence, and continuously introducing air for 15 min; then reacting for 8h at 50 ℃, exposing the reaction solution to air after the reaction is finished, stopping the reaction, adding ethanol for dilution, and removing the copper catalyst through a 60-200 mesh silica column; removing most of methanol and ethanol by rotary evaporation, adding hexane, precipitating polymer, filtering to obtain P (MeO)2MA-co-OEGMA-S-S-MeO2MA-co-OEGMA) polymer; mixing 1g P (MeO)2MA-co-OEGMA-S-S-MeO2MA-co-OEGMA) was dissolved in 15mL of dichloromethane, 400. mu.L (0.33g) of tributylphosphine was added as a reduction catalyst at room temperature, the mixture was rapidly stirred for 30 minutes, and the solvent was removed by rotary evaporation to obtain a monosulfided polymer P (MeO)2MA-co-OEGMA-SH)。
Preferably, the stainless steel net has a specification of 500-1800 meshes.
Preferably, the stainless steel mesh is cleaned by the following steps: cutting the stainless steel net to a required size, soaking the stainless steel net in dilute hydrochloric acid with the mass fraction of 15-20% until most of the surface just generates bubbles to remove a surface oxidation layer, then carrying out ultrasonic cleaning in deionized water, absolute ethyl alcohol and acetone for 10-15 minutes respectively in sequence, and drying for later use.
Preferably, the step (1) is specifically: soaking the cleaned stainless steel net in tris (hydroxymethyl) aminomethane buffer (10-15 mmol/l, pH 8.5); then adding dopamine hydrochloride, standing and reacting for 40-50 hours at room temperature, taking out and repeatedly washing with deionized water; and finally, drying for 12 hours in vacuum at the temperature of 40-50 ℃ to obtain the stainless steel net with the surface coated with the polydopamine.
Preferably, the step (2) is specifically: preparing 0.3-0.6 mol/L graphene oxide aqueous dispersion, soaking the stainless steel mesh coated with polydopamine on the surface prepared in the step (1) in the aqueous dispersion, reacting for 5-8 hours at 40-45 ℃, taking out, repeatedly washing with deionized water, and vacuum drying for 12 hours at 40-50 ℃ to prepare the graphene oxide/polydopamine coated stainless steel mesh.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the special wetting polymer is coated on the stainless steel mesh substrate with higher mechanical strength, and graphene oxide is more firmly locked on the stainless steel mesh coated on the surface of polydopamine, so that the prepared super-hydrophilic oil-water separation membrane has good mechanical property and long service life; the preparation method is simple and easy to implement, low in cost, wide in application range and wide in application prospect.
Detailed Description
In order to clearly illustrate the technical features of the present solution, the present solution is explained below by way of specific embodiments.
Example 1 preparation method of graphene oxide/polydopamine surface-coated stainless steel mesh
The embodiment of the invention provides a preparation method of a graphene oxide/polydopamine surface-coated stainless steel mesh, which comprises the following steps:
cutting a stainless steel net with the specification of 600 meshes into a square net with the side length of 10cm, soaking the square net in dilute hydrochloric acid with the mass fraction of 15% until most of the surface of the square net just generates bubbles so as to remove a surface oxide layer, then carrying out ultrasonic cleaning in deionized water, absolute ethyl alcohol and acetone for 10 minutes respectively in sequence, and drying for later use;
soaking the cleaned stainless steel net in tris (hydroxymethyl) aminomethane buffer (15 mmol/l, pH 8.5); then adding 1300mg of dopamine hydrochloride, standing at room temperature for reaction for 40 hours, taking out and repeatedly washing with deionized water; and finally, drying for 12 hours in vacuum at the temperature of 45 ℃ to obtain the stainless steel net with the surface coated with the polydopamine.
And (2) preparing 0.3 mol/L graphene oxide aqueous dispersion, soaking the stainless steel mesh coated with the polydopamine on the surface, prepared in the step (1), in the aqueous dispersion, reacting for 7 hours at 42 ℃, taking out the stainless steel mesh, repeatedly washing the stainless steel mesh with deionized water, and performing vacuum drying for 12 hours at 45 ℃ to prepare the graphene oxide/polydopamine surface-coated stainless steel mesh.
Example 2 preparation method of graphene oxide/polydopamine surface-coated stainless steel mesh
The embodiment of the invention provides a preparation method of a graphene oxide/polydopamine surface-coated stainless steel mesh, which comprises the following steps:
cutting a stainless steel net with the specification of 1200 meshes into a square net with the side length of 10cm, soaking the square net in 20% of dilute hydrochloric acid by mass fraction until most of the surface of the square net just generates bubbles to remove a surface oxide layer, then carrying out ultrasonic cleaning in deionized water, absolute ethyl alcohol and acetone for 12 minutes respectively in sequence, and drying for later use;
soaking the cleaned stainless steel mesh in tris (hydroxymethyl) aminomethane buffer (10 mmol/l, pH 8.5); then adding 1500mg of dopamine hydrochloride, standing at room temperature for reaction for 50 hours, taking out, and repeatedly washing with deionized water; and finally, drying for 12 hours in vacuum at 40 ℃ to obtain the stainless steel net with the surface coated with the polydopamine.
And (2) preparing 0.6 mol/L graphene oxide aqueous dispersion, soaking the stainless steel mesh coated with the polydopamine on the surface, prepared in the step (1), in the aqueous dispersion, reacting for 8 hours at 40 ℃, taking out the stainless steel mesh, repeatedly washing the stainless steel mesh with deionized water, and performing vacuum drying for 12 hours at 40 ℃ to prepare the graphene oxide/polydopamine surface-coated stainless steel mesh.
Example 3 preparation method of graphene oxide/polydopamine surface-coated stainless steel mesh
The embodiment of the invention provides a preparation method of a graphene oxide/polydopamine surface-coated stainless steel mesh, which comprises the following steps:
cutting a stainless steel net with the specification of 1800 meshes into a square net with the side length of 10cm, soaking the square net in 17% of dilute hydrochloric acid by mass fraction until most of the surface of the square net just generates bubbles to remove a surface oxide layer, then carrying out ultrasonic cleaning in deionized water, absolute ethyl alcohol and acetone for 15 minutes respectively in sequence, and drying for later use;
soaking the cleaned stainless steel mesh in tris (hydroxymethyl) aminomethane buffer (12 mmol/l, pH 8.5); then 1000mg of dopamine hydrochloride is added, standing and reacting are carried out for 45 hours at room temperature, and the mixture is taken out and repeatedly washed by deionized water; and finally, drying for 12 hours in vacuum at 50 ℃ to obtain the stainless steel net with the surface coated with the polydopamine.
And (2) preparing 0.5 mol/L graphene oxide aqueous dispersion, soaking the stainless steel mesh coated with the polydopamine on the surface, prepared in the step (1), in the aqueous dispersion, reacting for 5 hours at 45 ℃, taking out the stainless steel mesh, repeatedly washing the stainless steel mesh with deionized water, and performing vacuum drying for 12 hours at 50 ℃ to prepare the graphene oxide/polydopamine surface-coated stainless steel mesh.
Example 4-6 preparation method of Polymer-modified graphene filtration Membrane
Embodiments 4 to 6 of the present invention provide a method for preparing a polymer-modified graphene filtration membrane, including the following steps:
polymerizing polymer P (MeO)2MA-co-OEGMA-SH) is dissolved in Bicine buffer solution with the pH of 8.0 and the concentration of 0.15M and is uniformly mixed, then a stainless steel mesh coated on the surface of the oxidized graphene/polydopamine prepared in the embodiment 1 to 3 is placed in the solution in sequence and is stirred for 20 hours at room temperature, so that the tail end of the stainless steel mesh is provided with sulfydrylPolymer P (MeO)2MA-co-OEGMA-SH) was grafted onto a stainless steel mesh coated on the surface of graphene oxide/polydopamine to prepare the super-hydrophilic polymer-modified graphene filtration membranes of examples 4 to 6.
Example 7-9 preparation method of Polymer-modified graphene filtration Membrane
Embodiments 7 to 9 of the present invention provide a method for preparing a polymer-modified graphene filtration membrane, including the following steps:
polymerizing polymer P (MeO)2MA-co-OEGMA-SH) was dissolved in Bicine buffer solution having a pH of 9.0 and a concentration of 0.05M, and then, a stainless steel mesh coated on the surface of graphene oxide/polydopamine prepared in example 1 to 3 was sequentially placed in the solution and stirred at room temperature for 30 hours, thereby preparing a polymer P (MeO) having a thiol group at the end2MA-co-OEGMA-SH) on a stainless steel net coated on the surface of graphene oxide/polydopamine to prepare the super-hydrophilic polymer modified graphene filtering membranes of the embodiments 7 to 9.
Example 10-12 preparation method of Polymer-modified graphene filtration Membrane
Embodiments 10 to 12 of the present invention provide a method for preparing a polymer-modified graphene filtration membrane, including the following steps:
polymerizing polymer P (MeO)2MA-co-OEGMA-SH) was dissolved in Bicine buffer solution having a pH of 8.5 and a concentration of 0.1M, and then, the graphene oxide/polydopamine surface-coated stainless steel mesh prepared in example 1-3 was sequentially placed in the solution and stirred at room temperature for 36 hours, thereby preparing a polymer P (MeO) having a thiol group at the end2MA-co-OEGMA-SH) on a stainless steel net coated on the surface of graphene oxide/polydopamine to prepare the super-hydrophilic polymer modified graphene filtering membranes of the examples 10 to 12.
Examples of the experiments
In the experimental example of the present invention, the stainless steel mesh coated on the surface of the graphene oxide/polydopamine prepared in examples 1 to 3 and the polymer-modified graphene filtration membranes prepared in examples 4 to 12 are respectively used as oil-water filtration membranes, oil field sewage is filtered through the filtration membranes, and oil contents before and after filtration are detected, wherein the oil contents after filtration are respectively detected by samples after filtration at 10 minutes and 500 minutes of operation, and specific experimental data are shown in table 1. As can be seen from table 1, the oil-water separation efficiency of the polymer modified graphene filtration membrane of the present invention is very high, and is maintained at more than 97%, and is higher than that of the stainless steel mesh coated on the surface of the graphene oxide/polydopamine without polymer modification; when the membrane is operated for 500 minutes, the separation efficiency of the stainless steel net coated on the surface of the graphene oxide/polydopamine without the polymer modification as a filtering membrane is remarkably reduced, and the oil-water separation efficiency of the graphene filtering membrane modified by the polymer is still kept above 97%. After the stainless steel mesh coated on the surface of the graphene oxide/polydopamine without the polymer modification is used for a long time, the graphene oxide on the surface of the substrate falls off, so that the oil-water separation efficiency is reduced. Therefore, the graphene filtering membrane modified by the high polymer is high in oil-water separation efficiency and long in service life.
TABLE 1 oil field sewage separation efficiency test results
The technical features of the present invention which are not described in the above embodiments may be implemented by or using the prior art, and are not described herein again, of course, the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and variations, modifications, additions or substitutions which may be made by those skilled in the art within the spirit and scope of the present invention should also fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of a high-molecular modified graphene filtering membrane is characterized by comprising the following steps:
step (1), coating polydopamine on the surface of the stainless steel net after cleaning treatment;
reacting the stainless steel net coated with the polydopamine on the surface in the step (1) with graphene oxide to obtain a graphene oxide/polydopamine surface-coated stainless steel net;
step (3) adding polymer P (MeO) with sulfhydryl at end through Michael addition reaction under alkaline condition2MA-co-OEGMA-SH) to be grafted on a stainless steel net coated on the surface of the graphene oxide/polydopamine prepared in the step (2) to prepare a super-hydrophilic polymer modified graphene filtering membrane;
wherein the step (2) specifically comprises: preparing 0.3-0.6 mol/L graphene oxide aqueous dispersion, soaking the stainless steel mesh coated with polydopamine on the surface prepared in the step (1) in the aqueous dispersion, reacting for 5-8 hours at 40-45 ℃, taking out, repeatedly washing with deionized water, and vacuum drying for 12 hours at 40-50 ℃ to prepare the graphene oxide/polydopamine coated stainless steel mesh.
2. The method for producing a polymer-modified graphene filtration membrane according to claim 1, wherein the Michael addition reaction in the step (3) is carried out in a Bicine buffer solution having a pH of 8.0 to 9.0 and a concentration of 0.05 to 0.15M.
3. The method for preparing a polymer-modified graphene filtration membrane according to claim 1, wherein the Michael addition reaction in the step (3) is specifically: polymerizing polymer P (MeO)2MA-co-OEGMA-SH) is dissolved in Bicine buffer solution and uniformly mixed, then a stainless steel net coated on the surface of the oxidized graphene/polydopamine is placed in the solution, and the solution is stirred for 18 to 36 hours at room temperature, so that the high-molecular modified graphene filtering membrane can be obtained.
4. The polymer-modified graphene filter of claim 1A method for producing a film, wherein the polymer P (MeO) in the step (3)2MA-co-OEGMA-SH) preparation method comprises the following steps: 2-methyl-2-acrylic acid-2 (2-methoxyethoxy) ethyl ester and oligo-polyethylene glycol methyl ether methacrylate are taken as monomers, and bis [2- (2' -bromo-isobutyryloxy) ethyl]Synthesizing P (MeO) by atom transfer radical polymerization reaction by using disulfide as initiator, cuprous bromide as catalyst and 2, 2' -bipyridine as ligand2MA -co-OEGMA-S-S-MeO2MA-co-OEGMA) copolymer; then tributyl phosphine is used as a reduction catalyst to break disulfide bonds in the polymer to obtain a polymer P (MeO) with a sulfhydryl group at the end2MA-co-OEGMA-SH）。
5. The method for preparing a polymer-modified graphene filtration membrane according to claim 4, wherein the molecular weight of the oligo (ethylene glycol methyl ether) methacrylate is 475 g/mol.
6. The method for preparing a polymer-modified graphene filtration membrane according to claim 4, wherein the feeding molar ratio of the monomer 2-methyl-2-propenoic acid-2 (2 methoxyethoxy) ethyl ester to the oligoethylene glycol monomethyl ether methacrylate is 5: 1-20:1, initiator bis [2- (2' -bromo isobutyryloxy) ethyl]The using amount of disulfide is 1/150-1/50 of the molar weight of 2- (2 methoxyethoxy) ethyl 2-methyl-2-acrylate monomer, the using amount of cuprous bromide serving as a catalyst is 1/50-1/15 of the molar weight of 2- (2 methoxyethoxy) ethyl 2-methyl-2-acrylate monomer, the using amount of 2, 2' -bipyridyl serving as a ligand is 0.5-3 times of the molar weight of the catalyst, and the using amount of tributylphosphine is P (MeO)2MA -co-OEGMA-S-S- MeO2MA-co-OEGMA) 1/4-1/2.
7. The method for preparing a polymer-modified graphene filtration membrane according to any one of claims 1 to 4, wherein the stainless steel mesh has a specification of 500-1800 mesh.
8. The method for preparing a polymer modified graphene filtration membrane according to any one of claims 1 to 4, wherein the stainless steel mesh is cleaned by the following steps: cutting the stainless steel net to a required size, soaking the stainless steel net in dilute hydrochloric acid with the mass fraction of 15-20% until most of the surface just generates bubbles to remove a surface oxidation layer, then carrying out ultrasonic cleaning in deionized water, absolute ethyl alcohol and acetone for 10-15 minutes respectively in sequence, and drying for later use.
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Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990015883A1 (en) * | 1989-06-14 | 1990-12-27 | University Of Utah | Dna sequencing using low fluorescence background electroblotting membrane |
| CN103183340A (en) * | 2013-03-27 | 2013-07-03 | 复旦大学 | Ultra-high-modulus and high-strength oxidized graphene film and preparation method thereof |
| CN103424449A (en) * | 2013-07-30 | 2013-12-04 | 浙江理工大学 | Ferrocene grafted chitosan-carbon nanotube-enzyme composite membrane modified three-dimensional graphene composite material and preparation method thereof |
| CN103613724A (en) * | 2013-11-15 | 2014-03-05 | 无锡中科光远生物材料有限公司 | Preparation method for polylactic acid block copolymer micelle capable of slowly releasing medicines |
| CN104530332A (en) * | 2015-01-31 | 2015-04-22 | 济南大学 | Temperature-sensitive nano aquagel, and preparation method and application thereof |
| CN105030672A (en) * | 2015-07-27 | 2015-11-11 | 同济大学 | Method for preparing temperature-sensitive stereocomplex polylactic acid copolymer drug-loaded micell |
| CN105664738A (en) * | 2016-04-11 | 2016-06-15 | 江西师范大学 | Graphene oxide-based composite membrane for treating radioactive wastewater |
| CN105926366A (en) * | 2016-05-19 | 2016-09-07 | 山东交通学院 | Temperature-responsive oil-water separation filter paper and preparation method thereof |
| CN105968277A (en) * | 2016-05-13 | 2016-09-28 | 南京邮电大学 | {0><}0{>Multi-tooth sulfydryl two-block copolymer as well as preparation method and application thereof |
| CN106422816A (en) * | 2016-09-22 | 2017-02-22 | 华中科技大学 | Preparation method of graphene foam-polydopamine composite membrane, product prepared with preparation method and application of product |
| CN106589270A (en) * | 2016-11-23 | 2017-04-26 | 同济大学 | Preparation method of star polymer-based drug carrier material with fluorescence labeling and temperature responsiveness |
| CN106807338A (en) * | 2016-12-27 | 2017-06-09 | 中国石油大学(华东) | A kind of modified graphene for water-oil separating strengthens the preparation method of polyurethane sponge |
| CN106823861A (en) * | 2017-02-09 | 2017-06-13 | 浙江大学 | A kind of hollow fiber compound nanofiltration membrane based on natural polymer and preparation method thereof |
| CN106943896A (en) * | 2017-03-29 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation of three-dimensional porous graphene functionalized assembly membrane material and application process |
| CN107158980A (en) * | 2017-06-07 | 2017-09-15 | 浙江大学 | Utilized thin film composite membranes reacted based on air liquid interface and its preparation method and application |
| CN107188569A (en) * | 2017-06-18 | 2017-09-22 | 长沙无道工业设计有限公司 | A kind of desalinization composite membrane based on graphene oxide and preparation method thereof |
| CN108042800A (en) * | 2017-11-16 | 2018-05-18 | 华中科技大学 | Bivalent state platinum cluster of temperature sensitive polymer modification and its preparation method and application |
| TW201821282A (en) * | 2016-09-28 | 2018-06-16 | 日商三菱瓦斯化學股份有限公司 | Optical polyester film and transparent conductive film |
| CN108479118A (en) * | 2018-06-05 | 2018-09-04 | 中国石油大学(华东) | A kind of water-oil separating steel wire of graphene oxide/poly-dopamine surface modification |
| CN108479415A (en) * | 2018-04-16 | 2018-09-04 | 深圳弗尔斯特环境健康技术有限公司 | A kind of compound membrane for water treatment of graphene oxide and preparation method thereof |
| WO2018160871A2 (en) * | 2017-03-01 | 2018-09-07 | Nitto Denko Corporation | Selectively permeable graphene oxide membrane |
| CN108752530A (en) * | 2018-05-09 | 2018-11-06 | 同济大学 | It can the temperature-sensitive hydrogel materials of load cells, temperature-sensitive hydrogel and the preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017124572A1 (en) * | 2016-01-22 | 2017-07-27 | 南京理工大学 | Ultrafiltration membrane and preparation method therefor |
-
2018
- 2018-12-17 CN CN201811544413.0A patent/CN111318172B/en active Active
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990015883A1 (en) * | 1989-06-14 | 1990-12-27 | University Of Utah | Dna sequencing using low fluorescence background electroblotting membrane |
| CN103183340A (en) * | 2013-03-27 | 2013-07-03 | 复旦大学 | Ultra-high-modulus and high-strength oxidized graphene film and preparation method thereof |
| CN103424449A (en) * | 2013-07-30 | 2013-12-04 | 浙江理工大学 | Ferrocene grafted chitosan-carbon nanotube-enzyme composite membrane modified three-dimensional graphene composite material and preparation method thereof |
| CN103613724A (en) * | 2013-11-15 | 2014-03-05 | 无锡中科光远生物材料有限公司 | Preparation method for polylactic acid block copolymer micelle capable of slowly releasing medicines |
| CN104530332A (en) * | 2015-01-31 | 2015-04-22 | 济南大学 | Temperature-sensitive nano aquagel, and preparation method and application thereof |
| CN105030672A (en) * | 2015-07-27 | 2015-11-11 | 同济大学 | Method for preparing temperature-sensitive stereocomplex polylactic acid copolymer drug-loaded micell |
| CN105664738A (en) * | 2016-04-11 | 2016-06-15 | 江西师范大学 | Graphene oxide-based composite membrane for treating radioactive wastewater |
| CN105968277A (en) * | 2016-05-13 | 2016-09-28 | 南京邮电大学 | {0><}0{>Multi-tooth sulfydryl two-block copolymer as well as preparation method and application thereof |
| CN105926366A (en) * | 2016-05-19 | 2016-09-07 | 山东交通学院 | Temperature-responsive oil-water separation filter paper and preparation method thereof |
| CN106422816A (en) * | 2016-09-22 | 2017-02-22 | 华中科技大学 | Preparation method of graphene foam-polydopamine composite membrane, product prepared with preparation method and application of product |
| TW201821282A (en) * | 2016-09-28 | 2018-06-16 | 日商三菱瓦斯化學股份有限公司 | Optical polyester film and transparent conductive film |
| CN106589270A (en) * | 2016-11-23 | 2017-04-26 | 同济大学 | Preparation method of star polymer-based drug carrier material with fluorescence labeling and temperature responsiveness |
| CN106807338A (en) * | 2016-12-27 | 2017-06-09 | 中国石油大学(华东) | A kind of modified graphene for water-oil separating strengthens the preparation method of polyurethane sponge |
| CN106823861A (en) * | 2017-02-09 | 2017-06-13 | 浙江大学 | A kind of hollow fiber compound nanofiltration membrane based on natural polymer and preparation method thereof |
| WO2018160871A2 (en) * | 2017-03-01 | 2018-09-07 | Nitto Denko Corporation | Selectively permeable graphene oxide membrane |
| CN106943896A (en) * | 2017-03-29 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation of three-dimensional porous graphene functionalized assembly membrane material and application process |
| CN107158980A (en) * | 2017-06-07 | 2017-09-15 | 浙江大学 | Utilized thin film composite membranes reacted based on air liquid interface and its preparation method and application |
| CN107188569A (en) * | 2017-06-18 | 2017-09-22 | 长沙无道工业设计有限公司 | A kind of desalinization composite membrane based on graphene oxide and preparation method thereof |
| CN108042800A (en) * | 2017-11-16 | 2018-05-18 | 华中科技大学 | Bivalent state platinum cluster of temperature sensitive polymer modification and its preparation method and application |
| CN108479415A (en) * | 2018-04-16 | 2018-09-04 | 深圳弗尔斯特环境健康技术有限公司 | A kind of compound membrane for water treatment of graphene oxide and preparation method thereof |
| CN108752530A (en) * | 2018-05-09 | 2018-11-06 | 同济大学 | It can the temperature-sensitive hydrogel materials of load cells, temperature-sensitive hydrogel and the preparation method and application thereof |
| CN108479118A (en) * | 2018-06-05 | 2018-09-04 | 中国石油大学(华东) | A kind of water-oil separating steel wire of graphene oxide/poly-dopamine surface modification |
Non-Patent Citations (2)
| Title |
|---|
| Surface modification of UHMWPE/fabric composite membrane via self-polymerized polydopamine followed by mPEG-NH2 immobilization;Liu,Rong；Wang,Xinwei;《JOURNAL OF APPLIED POLYMER SCIENCE》;20180710;第135卷(第26期) * |
| Wear properties of graphene edges probed by atomic force microscopy based lateral manipulation;Vasic,Borislav；Matkovic,Aleksandar;《CARBON》;20161031;第107卷 * |
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