CN113493961A - Efficient oil-water separation nanofiber membrane and preparation method and application thereof - Google Patents
Efficient oil-water separation nanofiber membrane and preparation method and application thereof Download PDFInfo
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- D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
- D06M14/10—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention relates to the field of oil-water separation materials, and provides a high-efficiency oil-water separation nanofiber membrane and a preparation method and application thereof. According to the invention, the initiator MEBr is input into the high molecular polymer in a covalent bond mode, then the fiber membrane is prepared by an electrostatic spinning method, and the hydrophilic monomer and the surface and the interior of the fiber membrane are subjected to ATRP polymerization reaction, so that the hydrophilic modification of the fiber membrane by the hydrophilic monomer is realized, the hydration effect of the fiber membrane is enhanced, and the membrane flux, the oil-water separation efficiency and the stability of the fiber membrane are greatly improved.
Description
Technical Field
The invention relates to the field of oil-water separation materials, in particular to a high-efficiency oil-water separation nanofiber membrane and a preparation method and application thereof.
Background
Oil-water separation is an important method for solving the pollution of industrial oily wastewater and oil spill and protecting the environment. It not only has scientific research value, but also has practical application value. Therefore, it is imperative to develop functional materials for efficiently treating oily sewage.
For the treatment of oily wastewater, the traditional separation technology mainly comprises gravity separation, air flotation, coagulation, demulsification and the like, but has the defects of low separation efficiency, high energy consumption, complex operation process, serious secondary pollution, poor emulsion separation effect and the like. The membrane separation technology has the characteristics of high separation efficiency and simple operation, and is widely concerned.
Currently, superhydrophilic membranes are mainly prepared by surface modification, such as surface coating and surface grafting. However, the modified membrane surface is unstable and easily falls off, and the hydrophilicity gradually decreases. For oil-water separation, a more stable hydration layer is needed to prevent oil droplets from contacting the surface of the membrane matrix, resulting in a membrane with higher separation efficiency and stability.
Disclosure of Invention
The efficient oil-water separation nanofiber membrane provided by the invention has the advantages of high membrane flux, high oil-water separation efficiency, higher separation efficiency after circulation for many times and better stability.
The invention provides a preparation method of a high-efficiency oil-water separation nanofiber membrane, which comprises the following steps:
(1) under the protection atmosphere, mixing acrylonitrile, methyl methacrylate and dimethyl sulfoxide, heating to the polymerization reaction temperature, adding initiators MEBr and azobisisobutyronitrile, and carrying out polymerization reaction to obtain a spinning solution;
the structure of the initiator MEBr is shown as formula I:
(2) preparing the spinning solution obtained in the step (1) into a film by adopting an electrostatic spinning method to obtain a fibrous film;
(3) under a protective atmosphere, mixing a hydrophilic monomer, 2' -bipyridine, CuBr and a solvent to obtain a mixed solution; and (3) immersing the fiber membrane obtained in the step (2) in a mixed solution for ATRP polymerization reaction to obtain the high-efficiency oil-water separation nanofiber membrane.
Preferably, in the step (1), the mass ratio of acrylonitrile to methyl methacrylate to the initiator MEBr to the azobisisobutyronitrile is 10-20: 0.1-0.5: 1-3: 0.1-0.3, and the mass concentration of the initiator MEBr in the spinning solution is 5-35%.
Preferably, the polymerization reaction temperature in the step (1) is 60-76 ℃, and the polymerization reaction time is 4-10 h.
Preferably, the voltage of the electrostatic spinning method in the step (2) is 5-30 kV, the injection rate is 0.2-2 mL/h, and the receiving distance is 15-30 cm.
Preferably, the diameter of the fiber in the fiber membrane obtained in the step (2) is 100-1000 nm.
Preferably, the hydrophilic monomer in the step (3) includes 2[ - (methacryloyloxy) ethyl ] dimethyl (3-sulfopropyl) ammonium hydroxide monomer, N-isopropylacrylamide monomer, 3-sulfopropylpotassium methacrylate monomer, or methacryloyloxyethyl trimethylammonium chloride monomer.
Preferably, the dosage ratio of the hydrophilic monomer, the 2,2' -bipyridine, the CuBr and the solvent in the step (3) is 2-6 g: 80-160 mg: 10-50 mg:8 mL.
Preferably, the ATRP polymerization reaction temperature is 15-35 ℃ and the time is 1-6 h.
The invention also provides the high-efficiency oil-water separation nanofiber membrane prepared by the preparation method in the technical scheme.
The invention also provides an application of the high-efficiency oil-water separation nanofiber membrane in the technical scheme as an oil-water separation membrane.
Has the advantages that:
according to the invention, the initiator MEBr is input into the high molecular polymer in a covalent bond mode, then the fiber membrane is prepared by an electrostatic spinning method, and the hydrophilic monomer is subjected to ATRP polymerization reaction with the surface and the interior of the fiber membrane, so that the hydrophilic modification of the fiber membrane by the hydrophilic monomer is realized, the specific surface area of the fiber membrane is increased, the hydration effect is enhanced, and the membrane flux, the oil-water separation efficiency and the stability of the fiber membrane are greatly improved.
Drawings
FIG. 1 is a scanning electron micrograph of a nanofiber membrane obtained in the intermediate step of example 1;
FIG. 2 is a scanning electron microscope image of the high-efficiency oil-water separation nanofiber membrane obtained by ATRP polymerization modification in example 1 before and after water absorption;
fig. 3 is a graph of contact angles of oil-water separation nanofiber membranes prepared in example 1 and comparative example 1 with water drops in air;
fig. 4 is a graph of a cycle experiment of the oil-water separation nanofiber membrane prepared in comparative example 1.
Detailed Description
The invention provides a preparation method of a high-efficiency oil-water separation nanofiber membrane, which comprises the following steps:
(1) under the protection atmosphere, mixing acrylonitrile, methyl methacrylate and dimethyl sulfoxide, heating to the polymerization reaction temperature, adding initiators MEBr and azobisisobutyronitrile, and carrying out polymerization reaction to obtain a spinning solution;
The structure of the initiator MEBr is shown as formula I:
(2) preparing the spinning solution obtained in the step (1) into a film by adopting an electrostatic spinning method to obtain a fibrous film;
(3) under a protective atmosphere, mixing a hydrophilic monomer, 2' -bipyridine, CuBr and a solvent to obtain a mixed solution; and (3) immersing the fiber membrane obtained in the step (2) in a mixed solution for ATRP polymerization reaction to obtain the high-efficiency oil-water separation nanofiber membrane.
In the present invention, all the raw materials are commercially available products unless otherwise specified.
Under the protective atmosphere, acrylonitrile, methyl methacrylate and dimethyl sulfoxide are mixed and heated to the polymerization reaction temperature, and then initiators MEBr and azobisisobutyronitrile are added for polymerization reaction to obtain the spinning solution.
In the present invention, the polymerization reaction has the formula II:
in the invention, the mass ratio of the acrylonitrile to the methyl methacrylate to the initiator MEBr to the azobisisobutyronitrile is preferably 10-20: 0.1-0.5: 1-3: 0.1 to 0.3, more preferably 22.5:0.5:2: 0.18; the mass concentration of the initiator MEBr in the spinning solution is preferably 5-35%, more preferably 5-30%, and even more preferably 5-25%.
In the present invention, the preparation method of the initiator MEBr preferably comprises the following steps:
under the protection of nitrogen, reacting 2-bromoisobutyryl bromide, 2-hydroxyethyl methacrylate and triethylamine in dichloromethane to obtain an initiator MEBr; the molar ratio of the 2-bromoisobutyryl bromide to the 2-hydroxyethyl methacrylate is preferably 1:1, the reaction temperature is preferably 0-20 ℃, and the reaction time is preferably 3-7 h. After the reaction is complete, the reaction product is preferably washed with water to give the initiator MEBr.
In the invention, the polymerization reaction temperature is preferably 60-76 ℃, and more preferably 60-70 ℃; the time of the polymerization reaction is preferably 4-10 hours, and more preferably 6-8 hours. In the present invention, the protective atmosphere is preferably a nitrogen atmosphere. According to the invention, through the polymerization reaction, the initiator MEBr is introduced into the polymer in a covalent bond mode, and then the hydrophilic monomer is firmly fixed on the surface and inside of the fiber membrane through the subsequent reaction of the hydrophilic monomer and the initiator, so that the hydrophilic performance and the stability of the prepared high-efficiency oil-water separation nanofiber membrane are improved.
After the spinning solution is obtained, the invention adopts an electrostatic spinning method to prepare the spinning solution into a film, and a fiber film is obtained.
In the invention, the voltage of the electrostatic spinning method is preferably 5-30 kV, more preferably 10-25 kV, the injection rate is preferably 0.2-2 mL/h, more preferably 0.5-1.5 mL/h, and the receiving distance is preferably 15-30 cm, more preferably 20-30 cm. In the invention, the diameter of the fiber in the fiber membrane is preferably 100-1000 nm.
After the fiber membrane is obtained, the hydrophilic monomer, 2' -bipyridyl, CuBr and a solvent are mixed under a protective atmosphere to obtain a mixed solution.
In the present invention, the protective atmosphere is preferably a nitrogen atmosphere, and the hydrophilic monomer preferably includes a 2[ - (methacryloyloxy) ethyl ] dimethyl (3-sulfopropyl) ammonium hydroxide monomer, an N-isopropylacrylamide monomer, a 3-sulfopropylpotassium methacrylate monomer, or a methacryloyloxyethyltrimethylammonium chloride monomer. The hydrophilic monomer is preferably adopted, so that the hydrophilic performance and the stability of the finally prepared efficient oil-water separation nanofiber membrane are improved.
In the invention, the dosage ratio of the hydrophilic monomer, the 2,2' -bipyridine, the CuBr and the solvent is preferably 2-6 g: 80-160 mg: 10-50 mg:8mL, and more preferably 3-6 g: 100-160 mg: 20-50 mg:8 mL. In the invention, the solvent is preferably a mixed solvent of water and methanol or a mixed solvent of water and isopropanol, and the volume ratio of water to methanol in the mixed solvent of water and methanol is preferably 3: 2; the volume ratio of water to isopropanol in the mixed solvent of water and isopropanol is preferably 1: 3.
In the present invention, the hydrophilic monomer, 2' -bipyridine, CuBr, and the solvent are preferably mixed in a manner of: mixing a hydrophilic monomer with a solvent, introducing nitrogen to remove oxygen, adding 2,2' -bipyridine and CuBr, and continuously introducing nitrogen to obtain a mixed solution; the time for introducing nitrogen to remove oxygen is preferably 20-25 min, and the time for continuously introducing nitrogen is preferably 10-15 min. The invention preferably adopts the mixing mode, which is beneficial to fully removing oxygen in the mixed solution and avoiding the oxygen from influencing the ATRP polymerization reaction.
After the mixed solution is obtained, the fiber membrane is immersed in the mixed solution for ATRP polymerization reaction, and the high-efficiency oil-water separation nanofiber membrane is obtained.
In the invention, the ATRP polymerization reaction temperature is preferably 15-35 ℃, more preferably 15-30 ℃, and the time is preferably 1-6 h, more preferably 2-5 h. In the ATRP polymerization process, the hydrophilic monomer is polymerized under the catalysis of cuprous bromide and ligand 2,2' -bipyridyl.
According to the invention, preferably, after the ATRP polymerization reaction is finished, the fiber membrane after the reaction is taken out and washed by water, so that the high-efficiency oil-water separation nanofiber membrane is obtained.
According to the invention, the initiator MEBr is input into the high molecular polymer in a covalent bond mode, then the fiber membrane is prepared by an electrostatic spinning method, and the hydrophilic monomer is subjected to ATRP polymerization reaction with the surface and the interior of the fiber membrane, so that the hydrophilic modification of the fiber membrane by the hydrophilic monomer is realized, the specific surface area of the fiber membrane is increased, the hydration effect is enhanced, and the membrane flux, the oil-water separation efficiency and the stability of the fiber membrane are greatly improved.
The invention also provides the high-efficiency oil-water separation nanofiber membrane prepared by the preparation method in the technical scheme. The high-efficiency oil-water separation nanofiber membrane provided by the invention has a large specific surface area which can reach 420m2The large specific surface area is favorable for modifying the hydrophilicity of the nanofiber membrane, and a drop of 5 μ L of water needs only 6s to be completely absorbed on the membrane.
The invention also provides an application of the high-efficiency oil-water separation nanofiber membrane in the technical scheme as an oil-water separation membrane. The invention preferably uses the high-efficiency oil-water separation nanofiber membrane for separating an oil-water mixture of hexadecane and water.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Firstly, preparing an initiator 2- ((2-bromo-2-methylpropanoyl) oxy) ethyl methacrylate (MEBr) containing unsaturated double bonds: under the protection of nitrogen, 2-bromo isobutyryl bromide with equimolar amount reacts with 2-hydroxyethyl methacrylate and triethylamine in dichloromethane sufficiently under the condition of ice water bath, and then the initiator MEBr is obtained after the solvent is removed through multiple water washing and purification;
then preparing polyacrylonitrile spinning solution of the keyed initiator: adding 22.5g of acrylonitrile, 0.5g of methyl methacrylate and a solvent DMSO into a three-necked bottle with a reflux condenser tube, heating to 60 ℃ under the condition of introducing nitrogen, dropwise adding a mixed solution of an initiator MEBr and azobisisobutyronitrile (2g of MEBr and 0.18g of azobisisobutyronitrile) into the system, and continuously reacting for 10 hours to obtain a spinning solution;
Then receiving a nanofiber membrane with the average diameter of 520nm on an aluminum foil by an electrostatic spinning method under the voltage of 20kV, the injection rate of 0.7mL/h and the receiving distance of 20 cm;
finally, the modification of the polymer brush is carried out by means of an ATRP reaction: dissolving 4g of 2[ - (methacryloyloxy) ethyl ] dimethyl (3-sulfopropyl) ammonium hydroxide monomer in 8mL of water/methanol mixed solvent (the volume ratio of water to methanol is 3:2), introducing nitrogen to remove oxygen for 20min, adding 120mg of 2,2' -bipyridine and 40mg of CuBr, continuously introducing nitrogen for 10min, adding a nanofiber membrane to perform ATRP polymerization reaction at the reaction temperature of 20 ℃, taking out a sample after reacting for 4.5 hours, and washing with deionized water to obtain the high-efficiency oil-water separation nanofiber membrane.
Scanning electron microscope tests were performed on the nanofiber films obtained in the middle process of example 1, and the results are shown in fig. 1. As can be seen from FIG. 1, the nanofiber membrane of the present invention is successfully prepared by electrospinning, wherein a and b in FIG. 1 are SEM images of the nanofiber membrane under different magnifications.
Scanning electron microscope tests are carried out on the high-efficiency oil-water separation nanofiber membrane obtained by ATRP polymerization modification in example 1 before and after water absorption, and the results are shown in FIG. 2, wherein a in FIG. 2 is an SEM image of the high-efficiency oil-water separation nanofiber membrane before water absorption, a1 in FIG. 2 is an SEM image of the high-efficiency oil-water separation nanofiber membrane after water absorption, a2 in FIG. 2 is an SEM image of the high-efficiency oil-water separation nanofiber membrane at 1 μm after water absorption, and a3 in FIG. 2 is an SEM image of the high-efficiency oil-water separation nanofiber membrane at 100nm after water absorption. Fig. 2 shows that the nano fiber membrane after subsurface modification has obvious convex structure and increased specific surface area.
The flux change and the separation efficiency of the prepared high-efficiency oil-water separation nanofiber membrane in the separation of an oil-water mixture of hexadecane/water (volume ratio of 1:1) are tested, and the result shows that the membrane flux of the prepared high-efficiency oil-water separation nanofiber membrane under 1bar can reach 3620L m-2h-1The purity of the collected oil is detected by a Karl Fisher titrator (Metrohm 813KF, Switzerland), and the separation efficiency of the high-efficiency oil-water separation nanofiber membrane provided by the invention is more than 99.90 percent according to the water content in the separated oil; in the separation of an oil-water emulsion (sodium dodecyl sulfate-stabilized hexadecane/water emulsion where the ratio of the amount of sodium dodecyl sulfate, hexadecane and water is (10mg:1mL:100 mL)), the membrane flux under gravity alone is greater than 60Lm-2h-1And the COD content in the filtrate is 75 mg/L.
Example 2
Firstly, preparing an initiator MEBr according to the method of example 1;
then preparing polyacrylonitrile spinning solution of the keyed initiator: adding 22.5g of acrylonitrile, 0.5g of methyl methacrylate and a solvent DMSO into a three-necked bottle with a reflux condenser tube, heating to 60 ℃ under the condition of introducing nitrogen, dropwise adding a mixed solution of an initiator MEBr and azobisisobutyronitrile (2g of MEBr and 0.18g of azobisisobutyronitrile) into the system, and continuously reacting for 10 hours to obtain a spinning solution;
Then receiving the nanofiber membrane with the average diameter of 480nm on the aluminum foil by an electrostatic spinning method under the voltage of 15kV, the injection rate of 0.6mL/h and the receiving distance of 25cm, and drying in vacuum for later use;
finally, surface modification of the hydrophilic polymer brush is carried out by ATRP reaction: dissolving 3.5g of isopropyl acrylamide monomer in 8mL of mixed solvent of water/methanol (the volume ratio of water to methanol is 3:2), introducing nitrogen to remove oxygen for 20min, adding 100mg of 2,2' -bipyridine and 35mg of CuBr, continuously introducing nitrogen for 10min, adding the nanofiber membrane to perform ATRP polymerization reaction at the reaction temperature of 25 ℃, taking out a sample after reacting for 3 hours, and washing with deionized water to obtain the high-efficiency oil-water separation nanofiber membrane.
The flux change and the separation efficiency of the prepared high-efficiency oil-water separation nanofiber membrane in the separation of an oil-water mixture of hexadecane/water (volume ratio of 1:1) are tested, and the result shows that the membrane flux of the prepared high-efficiency oil-water separation nanofiber membrane can reach 3500L m-2h-1By detecting the purity of the collected oil by using a Karl Fisher titrator (Metrohm813KF, Switzerland), the separation efficiency of the high-efficiency oil-water separation nanofiber membrane provided by the invention is more than 98.50 percent according to the water content in the separated oil; when the separation of the oil-water emulsion is carried out on the hexadecane/water (volume ratio is 1:100) emulsion stabilized by the sodium dodecyl sulfate, the membrane flux under the gravity is more than 58Lm -2h-1And the COD content in the filtrate is 72 mg/L.
Example 3
Firstly, preparing an initiator MEBr according to the method of example 1;
then preparing polyacrylonitrile spinning solution of the keyed initiator: adding 22.5g of acrylonitrile, 0.5g of methyl methacrylate and a solvent DMSO into a three-necked bottle with a reflux condenser tube, heating to 60 ℃ under the condition of introducing nitrogen, dropwise adding a mixed solution of an initiator MEBr and azobisisobutyronitrile (2g of MEBr and 0.18g of azobisisobutyronitrile) into the system, and continuously reacting for 10 hours to obtain a spinning solution;
then receiving the nanofiber membrane with the average diameter of 680nm on the aluminum foil by an electrostatic spinning method under the voltage of 10kV, the injection rate of 1.0mL/h and the receiving distance of 30cm, and drying in vacuum for later use;
finally, PNIPAM polymer brush surface modification is carried out through ATRP reaction: in N26g of 3-sulfopropyl potassium methacrylate monomer is dissolved in a mixed solution of water and isopropanol (the volume ratio of the water to the isopropanol is 3:1) under the atmosphere to remove oxygen for 20min, 160mg of 2,2' -bipyridine and 50mg of CuBr are added, nitrogen is continuously introduced for 10min after continuous introduction, ATRP polymerization reaction is carried out on the nanofiber membrane after continuous introduction of nitrogen for 10min, the reaction temperature is 25 ℃, a sample is taken out after 2h of reaction, and the sample is washed by deionized water to obtain the high-efficiency oil-water separation nanofiber membrane.
The flux change and the separation efficiency of the prepared high-efficiency oil-water separation nanofiber membrane in the separation of an oil-water mixture of hexadecane/water (volume ratio of 1:1) are tested, and the result shows that the membrane flux of the prepared high-efficiency oil-water separation nanofiber membrane can reach 1850Lm at the temperature of 20 +/-2 DEG C-2h-1And the temperature is 45 ℃ +/-3 to 2867L m-2h-1By detecting the purity of the collected oil by a Karl Fisher titrator (Metrohm 813KF, Switzerland), the separation efficiency of the high-efficiency oil-water separation nanofiber membrane provided by the invention at the temperature of 20 +/-2 ℃ is 98.72 percent and at the temperature of 45 +/-3 ℃ is 9.13 percent according to the water content in the separated oil; when the separation of the oil-water emulsion is carried out on the hexadecane/water (volume ratio is 1:100) emulsion stabilized by the lauryl sodium sulfate, the membrane flux under the gravity is more than 65L m-2h-1And the COD content in the filtrate is 74 mg/L.
Example 4
Firstly, preparing an initiator MEBr according to the method of example 1;
then preparing polyacrylonitrile spinning solution of the keyed initiator: adding 22.5g of acrylonitrile, 0.5g of methyl methacrylate and a solvent DMSO into a three-necked bottle with a reflux condenser tube, heating to 60 ℃ under the condition of introducing nitrogen, dropwise adding a mixed solution of an initiator MEBr and azobisisobutyronitrile (2g of MEBr and 0.18g of azobisisobutyronitrile) into the system, and continuously reacting for 10 hours to obtain a spinning solution;
Then receiving the nano fiber membrane with the average diameter of 310nm on the aluminum foil by an electrostatic spinning method under the voltage of 20kV, the injection rate of 0.7mL/h and the receiving distance of 20cm, and drying in vacuum for later use;
finally, the modification of the polymer brush is carried out by means of an ATRP reaction: dissolving 4g of methacryloyloxyethyl trimethyl ammonium chloride monomer in 8mL of mixed solvent of water/methanol (the volume ratio of water to methanol is 3:2), introducing nitrogen to remove oxygen for 20min, adding 120mg of 2,2' -bipyridine and 40mg of CuBr, continuously introducing nitrogen for 10min, adding a nanofiber membrane to perform ATRP polymerization reaction at the reaction temperature of 20 ℃, taking out a sample after reaction for a period of time, and washing with deionized water to obtain the high-efficiency oil-water separation nanofiber membrane.
The flux change and the separation efficiency of the prepared high-efficiency oil-water separation nanofiber membrane in the separation of an oil-water mixture of hexadecane/water (the volume ratio is 1:1) are tested, and the result shows that the membrane flux of the prepared high-efficiency oil-water separation nanofiber membrane can reach 3750L m-2h-1By detecting the purity of the collected oil by using a Karl Fisher titrator (Metrohm813KF, Switzerland), the separation efficiency of the high-efficiency oil-water separation nanofiber membrane provided by the invention is more than 99.90 percent according to the water content in the separated oil; when the separation of the oil-water emulsion is carried out on the hexadecane/water (volume ratio is 1:100) emulsion stabilized by the sodium dodecyl sulfate, the membrane flux under the gravity is more than 62Lm -2h-1And the COD content in the filtrate is 75 mg/L.
Comparative example 1
Adopting a chlorosilane initiator, wherein the structure is shown as the following formula:
then preparing polyacrylonitrile spinning solution of the keyed initiator: adding 22.5g of acrylonitrile, 0.5g of methyl methacrylate and a solvent DMSO into a three-necked bottle with a reflux condenser tube, heating to 60 ℃ under the condition of introducing nitrogen, dropwise adding 0.18g of azobisisobutyronitrile into the system, and continuously reacting for 10 hours to obtain a spinning stock solution;
obtaining a fiber membrane under the conditions of voltage of 20kv, injection rate of 1mL/h and receiving distance of 20 cm;
and (3) anchoring chlorosilane initiator molecules on the fiber membrane on the surface of the membrane by a vapor deposition method, wherein the mass fraction of the chlorosilane initiator in the fiber membrane is 7%, so as to obtain the surface-modified oil-water separation nanofiber membrane.
The contact condition of the oil-water separation nanofiber membranes of example 1 and comparative example 1 with water drops in air is tested, and the results are shown in fig. 3, wherein a in fig. 3 is the test result of comparative example 1, and b in fig. 3 is the test result of example 1. As can be seen from fig. 3, the nanofiber membrane of example 1 has a higher water permeation rate.
When the oil-water separation nanofiber membrane obtained in comparative example 1 was tested for separation of a mixture of water and petroleum ether oil-water (the volume ratio of water to petroleum ether was 1:10), the separation effect after multiple cycles was shown in fig. 4. In FIG. 4, "PAN-g-PSBMA" is the result of the cycle test of comparative example 1, and "PAN-sg-PSBMA" is the result of the cycle test of example 1. As can be seen from fig. 4, the membrane flux decreased after 10 cycles of the oil-water separation nanofiber membrane provided in comparative example 1. However, the flux of the nanofiber membrane provided in example 1 remained stable after 10 cycles.
In conclusion, the high-efficiency oil-water separation nano-membrane provided by the invention has the advantages of high membrane flux, high oil-water separation efficiency, high separation efficiency after repeated circulation and good stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-efficiency oil-water separation nanofiber membrane comprises the following steps:
(1) under the protection atmosphere, mixing acrylonitrile, methyl methacrylate and dimethyl sulfoxide, heating to the polymerization reaction temperature, adding initiators MEBr and azobisisobutyronitrile, and carrying out polymerization reaction to obtain a spinning solution;
the structure of the initiator MEBr is shown as formula I:
(2) preparing the spinning solution obtained in the step (1) into a film by adopting an electrostatic spinning method to obtain a fibrous film;
(3) under a protective atmosphere, mixing a hydrophilic monomer, 2' -bipyridine, CuBr and a solvent to obtain a mixed solution; and (3) immersing the fiber membrane obtained in the step (2) in a mixed solution for ATRP polymerization reaction to obtain the high-efficiency oil-water separation nanofiber membrane.
2. The preparation method according to claim 1, wherein the mass ratio of acrylonitrile to methyl methacrylate to the initiator MEBr to azobisisobutyronitrile in the step (1) is 10-20: 0.1-0.5: 1-3: 0.1-0.3, and the mass concentration of the initiator MEBr in the spinning solution is 5-35%.
3. The method according to claim 1 or 2, wherein the polymerization temperature in step (1) is 60 to 76 ℃ and the polymerization time is 4 to 10 hours.
4. The method according to claim 1, wherein the electrospinning in the step (2) has a voltage of 5 to 30kV, an injection rate of 0.2 to 2mL/h, and a receiving distance of 15 to 30 cm.
5. The preparation method according to claim 1 or 4, wherein the diameter of the fiber in the fiber membrane obtained in the step (2) is 100-1000 nm.
6. The method according to claim 1, wherein the hydrophilic monomer in the step (3) comprises 2[ - (methacryloyloxy) ethyl ] dimethyl (3-sulfopropyl) ammonium hydroxide monomer, N-isopropylacrylamide monomer, 3-sulfopropyl potassium methacrylate monomer, or methacryloyloxyethyl trimethylammonium chloride monomer.
7. The preparation method according to claim 1, wherein the amount ratio of the hydrophilic monomer, the 2,2' -bipyridine, the CuBr and the solvent in the step (3) is 2-6 g: 80-160 mg: 10-50 mg:8 mL.
8. The method of claim 1, 6 or 7, wherein the ATRP polymerization reaction is carried out at a temperature of 15 to 35 ℃ for 1 to 6 hours.
9. The efficient oil-water separation nanofiber membrane prepared by the preparation method of any one of claims 1-8.
10. The use of the high efficiency oil-water separation nanofiber membrane of claim 9 as an oil-water separation membrane.
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