CN115845616A - COFs nano material mixed matrix ultrafiltration membrane based on Teleger base and preparation method thereof - Google Patents
COFs nano material mixed matrix ultrafiltration membrane based on Teleger base and preparation method thereof Download PDFInfo
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- CN115845616A CN115845616A CN202211641623.8A CN202211641623A CN115845616A CN 115845616 A CN115845616 A CN 115845616A CN 202211641623 A CN202211641623 A CN 202211641623A CN 115845616 A CN115845616 A CN 115845616A
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Abstract
The invention discloses a COFs nano material mixed matrix ultrafiltration membrane based on Teleger base and a preparation method thereof, wherein the COFs nano material mixed matrix ultrafiltration membrane comprises the following steps: constructing a solution containing a Teller's basic monomer with primary amine groups at two ends, and respectively mixing the solution with a trialdehyde phloroglucinol or trimeldehyde solution to prepare the COFs nano material; mixing and dissolving COFs nano-material, polysulfone base material and pore-foaming agent in an organic solvent to obtain a membrane casting solution; the casting solution is used for preparing the COFs nano material mixed matrix ultrafiltration membrane based on the Teller-Gease by a non-solvent induced phase separation method. The mixed matrix ultrafiltration membrane prepared by the invention realizes high-efficiency separation and purification of various proteins with different molecular weights, improves the protein interception performance of the ultrafiltration membrane, is convenient and stable to operate, has a simple preparation method, can be recycled for multiple times, has no secondary pollution, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a COFs nano-material mixed matrix ultrafiltration membrane based on Teleger bases and a preparation method thereof.
Background
The membrane separation technology is the most widely applied separation and purification technology with the greatest prospect at present, and the membrane separation process has the characteristics of no phase change, low energy consumption, high separation selectivity, simple process, easy operation and the like and is widely applied to the fields of food, medicine, biology, chemical production, sewage treatment, seawater desalination and the like. The membrane may be classified into a pressure driving membrane, an electric driving membrane, etc. according to the operation manner. Among them, the pressure driven membrane is classified into a micro filtration Membrane (MF), an ultrafiltration membrane (UF), a nanofiltration membrane (NF), and a reverse osmosis membrane (RO) according to the size of the membrane pore diameter and the separation capacity. The pore diameter of the ultrafiltration membrane is generally 5 nm-100 nm, and the ultrafiltration membrane is mainly used for intercepting molecular weight more than 1000g & mol -1 The substance of (1).
At present, most of the methods commonly used for separation and purification of proteins in biomedicine are physical and chemical methods such as precipitation, salting-out, chromatography, continuous centrifugation, filtration or extraction. Continuous centrifugation and chromatography techniques are still generally adopted in protein separation, but the protein molecules obtained by simple separation in the prior art generally have the defects of low purity, complex operation and the like; chemical purification methods such as precipitation, salting out, and extraction are easily damaged when purifying some substances with biological activity or heat sensitivity. The ultrafiltration technology belongs to the bioseparation and purification technology which is applied more at present, and the ultrafiltration and centrifugation method can realize the sieving, purification, concentration and the like of protein molecules with different molecular weights in a shorter time. At present, the demand on the ultrafiltration membrane with low molecular weight retention rate is large in China, but most membrane materials depend on import, the synthesis process is complex, and the cost is high, so that the development of the ultrafiltration membrane with low cost and low molecular weight retention has important practical significance.
Disclosure of Invention
The invention aims to provide a mixed matrix ultrafiltration membrane taking COFs nano materials based on Telleger base as blending materials and a preparation method thereof aiming at the defects of the preparation technology of the low molecular weight rejection rate ultrafiltration membrane in China.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a COFs nano material mixed matrix ultrafiltration membrane based on Teleger base comprises the following steps:
1) Taking a Teller-Ge base monomer with primary amine groups at two ends, adding glacial acetic acid to adjust the pH value to obtain a solution A; taking trialdehyde phloroglucinol or trimesic aldehyde in an organic solvent, and uniformly stirring to obtain a solution B;
2) Mixing the solution A and the solution B, uniformly stirring, and standing for reaction to generate COFs nano-materials to obtain a suspension C;
3) Standing and precipitating the suspension C, centrifuging, and retaining the precipitate; repeatedly cleaning and drying the precipitate to obtain COFs powder;
4) Preparing a casting solution: weighing a certain amount of COFs powder, dissolving the COFs powder in an organic solvent, performing ultrasonic crushing and dispersion to obtain a homogeneous solution, and then weighing a certain amount of polysulfone base material and a pore-forming agent, and adding the polysulfone base material and the pore-forming agent into the homogeneous solution to obtain a membrane casting solution; heating and stirring the obtained membrane casting solution at a certain temperature until the membrane casting solution is completely dissolved, continuing to heat after the membrane casting solution is uniformly stirred and mixed, and standing for defoaming;
5) Preparing an ultrafiltration membrane: pouring the casting solution completely defoamed on a glass plate carrier with non-woven fabrics, uniformly spreading the casting solution on the surfaces of the non-woven fabrics by using a scraper, and immediately putting the non-woven fabrics into a pure water bath for solidification to form a film; the prepared membrane was then soaked in ultrapure water.
The Teller base monomer with primary amine groups at two ends in the step 1) is TBDA, and the structural formulas of TBDA, TP and TBA are shown as follows:
in the step 1), after the Teller's basic group monomer with primary amine groups at two ends is dissolved in water, the solute concentration in the solution is 2.8-3.1wt%; adjusting the pH value to 3 by glacial acetic acid; the solute concentration in the solution B is 2.1-2.5wt%; the organic solvent is one of acetonitrile, dichloroethane, cyclohexane, n-hexane and n-heptane.
In the step 2), the solution A and the solution B are mixed according to the mass ratio of 1: 0.75-1.5.
The reaction equations for preparing COFs nano-materials in step 2) are respectively as follows:
in the step 4), the mass fraction of the polysulfone base material in the membrane casting solution is 15-30%, the mass fraction of the COFs nano material in the membrane casting solution is 1-20%, the mass fraction of the pore-foaming agent in the membrane casting solution is 1-10%, and the mass fraction of the organic solvent in the membrane casting solution is 50-80%.
In the step 4), the polysulfone base material is polysulfone or polyethersulfone; the pore-forming agent is one or more of PVPK15, PVPK25, PVPK30, PVPK60, PF127, PEG 300, PEG600, PEG 2000, PEG 4000 and LiCl.
In the step 4), the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
The thickness of the scraper in the step 5) is 100-250 μm; the temperature is 20-70 ℃ when the film is scraped.
The temperature of the pure water bath in the step 5) is 0-30 ℃.
The beneficial effects of the invention are: the invention prepares the mixed matrix ultrafiltration membrane which can be used for intercepting the low molecular weight protein by blending the COFs nano material, can realize the interception effect on the proteins with different molecular weights by parameters such as condition membrane casting liquid, membrane scraping condition and the like, and adjusts the aperture of the ultrafiltration membrane based on the better compatibility between the COFs nano material and the polysulfone polymer, thereby improving the protein interception performance of the ultrafiltration membrane; the product is prepared by adopting a non-solvent induced phase separation technology, the difficulty of the membrane preparation process is low, the production cost is low, the ultrafiltration membrane can be recycled for multiple times, no secondary pollution is caused, and the application prospect is good.
Drawings
FIG. 1 is a graph showing the comparison between an ultrafiltration membrane (a) prepared in example 1 of the present invention and an ultrafiltration membrane (b) prepared in comparative example 1.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples, and the examples are intended to be illustrative and not restrictive.
Example 1:
step 1: taking a Teller-Kwang base monomer (TBDA) with primary amine groups at two ends, adding glacial acetic acid to adjust the pH to be =3, and preparing a solution A, wherein the TBDA is a solution with the concentration of 2.8 wt%; taking Trialdehyde Phloroglucinol (TP) in acetonitrile, and uniformly stirring to prepare a solution B with the concentration of 2.1 wt%.
Step 2: and (3) mixing the solution A and the solution B according to the mass ratio of 1:1, mixing, uniformly stirring, and standing for half an hour to obtain a suspension C.
And step 3: standing the suspension C for precipitation, and centrifuging to retain the precipitate; and washing the precipitate with ethanol, drying in a vacuum oven, and repeatedly washing and drying to obtain the COFs powder.
And 4, step 4: preparing a casting solution: weighing a certain amount of COFs powder, dissolving the COFs powder in an N, N-dimethylformamide solvent, carrying out ultrasonic crushing and dispersing to obtain a homogeneous solution, and then weighing a certain amount of polyether sulfone PES and PVP K60, and adding the polyether sulfone PES and the PVP K60 into the homogeneous solution to obtain a membrane casting solution. Heating and stirring the obtained casting solution at a certain temperature until the casting solution is completely dissolved, continuing to heat after the casting solution is uniformly stirred and mixed, and standing for defoaming. Wherein the mass ratio of PES, COFs, PVP K60 and N, N-dimethylformamide is 16%, 0.5%, 3.5% and 80%.
And 5: preparing an ultrafiltration membrane: pouring the completely defoamed casting solution on a glass plate carrier with non-woven fabrics, uniformly spreading the casting solution on the surface of the non-woven fabrics by using a 250-micron scraper (controlling the temperature to be 20-70 ℃ during membrane scraping), and immediately putting the non-woven fabrics into a pure water bath (controlling the temperature to be 0-30 ℃) to solidify and form a membrane. The prepared membrane was immersed in ultrapure water.
Examples 2, 3:
examples 2 and 3 experimental procedures for preparing a mixed matrix ultrafiltration membrane example 1 was repeated except that the mass ratios of PES, COFs, PVP K30 and N, N-dimethylformamide in step 4 were 19%, 0.5%, 3.5% and 77%, respectively; 21%, 0.5%, 3.5%, 75%.
Comparative example 1:
step 1: preparing a casting solution: weighing a certain amount of PES and PVP K60, and adding into an N, N-dimethylformamide solvent to obtain a membrane casting solution. Heating and stirring the obtained casting solution at a certain temperature until the casting solution is completely dissolved, continuing to heat after the casting solution is uniformly stirred and mixed, and standing for defoaming. Wherein the mass ratio of PES, PVP K60 and N, N-dimethylformamide is 16%, 0.5%, 3.5% and 80%.
Step 2: preparing an ultrafiltration membrane: pouring the casting solution completely defoamed on a glass plate carrier with non-woven fabrics, uniformly spreading the casting solution on the surfaces of the non-woven fabrics by using a scraper, and immediately putting the non-woven fabrics into a pure water bath for solidification to form a film. The prepared membrane was immersed in ultrapure water.
Comparative examples 2, 3: the experimental process for preparing the mixed matrix ultrafiltration membrane is repeated in the comparative example 1, except that the mass ratio of PES, PVP K60 and N, N-dimethylformamide in the step 4 is 19%, 0.5%, 3.5% and 77%;21%, 0.5%, 3.5%, 75%.
Performance evaluation:
the performance test is carried out by combining the mixed matrix ultrafiltration membrane doped with the COFs nanospheres prepared in each embodiment example with a special centrifuge tube to form an ultrafiltration centrifuge tube. The centrifuge with a fixed angle rotor was used and the prepared test tubes were placed in a centrifuge and run at 5000Xg centrifugal force (approx. 7441 r/min) for 20 minutes. Among the substances used for the test are bovine serum albumin (BSAMw 67000), pepsin (Pepsin Mw 34500), lysozyme (Lysozyme Mw 14500), dextran20000 (Dextran 20000), dextran10000 (Dextran 10000), polyethylene glycol 8000 (PEG 8000), polyethylene glycol 6000 (PEG 6000), etc.
TABLE 1 evaluation of the Performance of the Ultrafiltration membranes prepared in the different examples
As can be seen from comparison between examples 1-3 and comparative examples 1-3, the mixed matrix membrane prepared by using the COFs nano material can effectively improve the retention capacity of the ultrafiltration membrane on substances with different molecular weights.
Example 4:
step 1: taking a Teller-base monomer (TBDA) with primary amine groups at two ends, placing the Teller-base monomer (TBDA) in water to prepare a solution with the concentration of 3.1wt%, and adding glacial acetic acid to adjust the pH to be =3 to obtain a solution A; taking trimesic aldehyde (TBA) in cyclohexane, and stirring uniformly to obtain a solution B with the concentration of 2.5 wt%.
Step 2: mixing the solution A and the solution B according to a mass ratio of 1:1.1, mixing, stirring evenly, standing and reacting for one hour to obtain suspension C.
And step 3: standing the suspension C for precipitation, and centrifuging and retaining the precipitate; and washing the precipitate with ethanol, drying in a vacuum oven, and repeatedly washing and drying to obtain the COFs powder.
And 4, step 4: preparing a casting solution: weighing a certain amount of COFs powder, dissolving the COFs powder in an N, N-dimethylformamide solvent, carrying out ultrasonic crushing and dispersing to obtain a homogeneous solution, and then weighing a certain amount of PES and PEG600, and adding the PES and the PEG600 into the homogeneous solution to obtain a membrane casting solution. Heating and stirring the obtained casting solution at a certain temperature until the casting solution is completely dissolved, continuing to heat after the casting solution is uniformly stirred and mixed, and standing for defoaming. Wherein the mass ratio of PES, COFs, PEG600 and N, N-dimethylformamide is 15%, 0.8%, 8.2% and 76%.
And 5: preparing an ultrafiltration membrane: pouring the casting solution which is completely defoamed on a glass plate carrier with non-woven fabrics, uniformly spreading the casting solution on the surface of the non-woven fabrics by using a 100-micron scraper (controlling the temperature to be 20-70 ℃ during film scraping), and immediately putting the non-woven fabrics into pure water bath (controlling the temperature to be 0-30 ℃) to solidify and form a film. The prepared membrane was immersed in ultrapure water.
Examples 5, 6:
examples 2, 3 experimental procedures for preparation of mixed matrix ultrafiltration membrane example 4 was repeated except that in step 4 the mass ratio of PES, COFs, PEG600 and N, N-dimethylformamide was 17.5%, 0.8%, 8.2%, 73.5%;21%, 0.8%, 8.2%, 70%.
Comparative example 4:
step 1: preparing a casting solution: weighing a certain amount of PES and PEG600, and adding the PES and the PEG600 into an N, N-dimethylformamide solvent to obtain a membrane casting solution. Heating and stirring the obtained casting solution at a certain temperature until the casting solution is completely dissolved, continuing to heat after the casting solution is uniformly stirred and mixed, and standing for defoaming. Wherein the mass ratio of PES, PEG600 and N, N-dimethylformamide is 15%, 8.2% and 76%.
Step 2: preparing an ultrafiltration membrane: pouring the casting solution completely defoamed on a glass plate carrier with non-woven fabrics, uniformly spreading the casting solution on the surfaces of the non-woven fabrics by using a 150-micron scraper, and immediately putting the non-woven fabrics into a pure water bath for solidification and film formation. The prepared membrane was immersed in ultrapure water.
Comparative examples 5, 6: the experimental process for preparing the mixed matrix ultrafiltration membrane is repeated in comparative example 4, except that the mass ratio of PES, PEG600 and N, N-dimethylformamide in step 4 is 17.5%, 8.2% and 73.5%;21%, 8.2% and 70%.
Performance evaluation:
performance evaluation of examples 4-6 and comparative examples 4-6 (same procedure as in examples 1-3 and comparative examples 1-3).
TABLE 2 evaluation of the Performance of the Ultrafiltration membranes prepared in the different examples
As can be seen from the comparison between examples 4-6 and comparative examples 4-6, the mixed matrix membrane prepared by using the COFs nano material can effectively improve the retention capacity of the ultrafiltration membrane on substances with different molecular weights.
In the invention, when the solution B is prepared in the step 1), the adopted organic solvent can be one of dichloroethane, n-hexane and n-heptane. The solution A and the solution B in the step 2) can be mixed according to the mass ratio of 1:0.75-1.5, to obtain COFs nanomaterials. When preparing the membrane casting solution in the step 4), the COFs powder can also be dissolved in one or more solvents of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide; polysulfone can also be used as polysulfone base material; the pore-forming agent can adopt one or more of PVP K15, PVP K25, PVP K30, PVP K60, PEG600, PF127, PEG 300, PEG 2000, PEG 4000 and LiCl besides the PVP K60 and PEG 600; based on the requirements for the retention effect of proteins of different molecular weights, the casting solution can be formulated as: the mass fraction of the polysulfone base material in the membrane casting solution is 15-30%, the mass fraction of the COFs nano material in the membrane casting solution is 1-20%, the mass fraction of the pore-forming agent in the membrane casting solution is 1-10%, and the mass fraction of the organic solvent in the membrane casting solution is 50-80%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should all embodiments be exhaustive. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A preparation method of a COFs nano material mixed matrix ultrafiltration membrane based on Teller basis is characterized by comprising the following steps:
1) Taking a Teller-Ge base monomer with primary amine groups at two ends, adding glacial acetic acid to adjust the pH value to obtain a solution A; taking trialdehyde phloroglucinol or trimesic aldehyde in an organic solvent, and uniformly stirring to obtain a solution B;
2) Mixing the solution A and the solution B, uniformly stirring, and standing to react to generate COFs nano-materials to obtain a suspension C;
3) Standing and precipitating the suspension C, centrifuging, and retaining the precipitate; repeatedly cleaning and drying the precipitate to obtain COFs powder;
4) Preparing a casting solution: weighing a certain amount of COFs powder, dissolving the COFs powder in an organic solvent, performing ultrasonic crushing and dispersion to obtain a homogeneous phase solution, and then weighing a certain amount of polysulfone base materials and a pore-forming agent, and adding the polysulfone base materials and the pore-forming agent into the homogeneous phase solution to obtain a membrane casting solution; heating and stirring the obtained membrane casting solution at a certain temperature until the membrane casting solution is completely dissolved, continuing to heat after the membrane casting solution is uniformly stirred and mixed, and standing for defoaming;
5) Preparing an ultrafiltration membrane: pouring the casting solution completely defoamed on a glass plate carrier with non-woven fabrics, uniformly spreading the casting solution on the surfaces of the non-woven fabrics by using a scraper, and immediately putting the non-woven fabrics into a pure water bath for solidification to form a film; the prepared membrane was then soaked in ultrapure water.
2. The method for preparing the COFs nano-material mixed matrix ultrafiltration membrane based on the Teller base in the step 1), wherein the Teller base monomer with primary amine groups at two ends in the step 1) is TBDA, and the structural formulas of TBDA, TP and TBA are as follows:
3. the COFs nano-material mixed matrix ultrafiltration membrane based on the Teller lattice base and the preparation method thereof of claim 1, wherein the COFs nano-material mixed matrix ultrafiltration membrane is characterized in that: in the step 1), after the Teller's basic group monomer with primary amine groups at two ends is dissolved in water, the solute concentration in the solution is 2.8-3.1wt%; adjusting the pH value to 3 by glacial acetic acid; the solute concentration in the solution B is 2.1-2.5wt%; the organic solvent is one of acetonitrile, dichloroethane, cyclohexane, n-hexane and n-heptane.
4. The COFs nano-material mixed matrix ultrafiltration membrane based on the Teller lattice base and the preparation method thereof of claim 1, wherein the COFs nano-material mixed matrix ultrafiltration membrane is characterized in that: in the step 2), the solution A and the solution B are mixed according to the mass ratio of 1: 0.75-1.5.
5. The method for preparing the COFs nano-material mixed matrix ultrafiltration membrane based on the Teller base according to the claim 1, wherein the reaction equations for preparing the COFs nano-material in the step 2) are respectively as follows:
6. the COFs nano-material mixed matrix ultrafiltration membrane based on the Teller lattice base and the preparation method thereof of claim 1, wherein the COFs nano-material mixed matrix ultrafiltration membrane is characterized in that: in the step 4), the mass fraction of the polysulfone base material in the membrane casting solution is 15-30%, the mass fraction of the COFs nano material in the membrane casting solution is 1-20%, the mass fraction of the pore-foaming agent in the membrane casting solution is 1-10%, and the mass fraction of the organic solvent in the membrane casting solution is 50-80%.
7. The COFs nano-material mixed matrix ultrafiltration membrane based on the Teller's base group and the preparation method thereof as claimed in claim 1, characterized in that: in the step 4), the polysulfone base material is polysulfone or polyethersulfone; the pore-forming agent is one or more of PVP K15, PVP K25, PVP K30, PVP K60, PF127, PEG 300, PEG600, PEG 2000, PEG 4000 and LiCl.
8. The COFs nano-material mixed matrix ultrafiltration membrane based on the Teller lattice base and the preparation method thereof of claim 1, wherein the COFs nano-material mixed matrix ultrafiltration membrane is characterized in that: in the step 4), the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
9. The COFs nano-material mixed matrix ultrafiltration membrane based on the Teller lattice base and the preparation method thereof of claim 1, wherein the COFs nano-material mixed matrix ultrafiltration membrane is characterized in that: the thickness of the scraper in the step 5) is 100-250 μm; the temperature is 20-70 ℃ when the film is scraped.
10. The COFs nano-material mixed matrix ultrafiltration membrane based on the Teller lattice base and the preparation method thereof of claim 1, wherein the COFs nano-material mixed matrix ultrafiltration membrane is characterized in that: the temperature of the pure water bath in the step 5) is 0-30 ℃.
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