CN113019149B - Acid-catalyzed COF self-assembled modified ultrafiltration membrane and preparation method thereof - Google Patents
Acid-catalyzed COF self-assembled modified ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN113019149B CN113019149B CN202110387184.1A CN202110387184A CN113019149B CN 113019149 B CN113019149 B CN 113019149B CN 202110387184 A CN202110387184 A CN 202110387184A CN 113019149 B CN113019149 B CN 113019149B
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
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Abstract
The invention discloses an acid-catalyzed COF self-assembled modified ultrafiltration membrane and a preparation method thereof, belonging to the technical field of organic hybrid separation. Dissolving polymer acid, a film substrate and PVP in an organic solvent to prepare a homogeneous solution, then sequentially putting aldehydes and amines for COF synthesis into the homogeneous solution, and stirring for reaction to prepare a uniform and stable coating solution; and (3) standing the coating liquid, defoaming, casting a membrane, and finally preparing the required ultrafiltration membrane by a non-solvent induced phase separation method. The acid-catalyzed COF self-assembled modified ultrafiltration membrane prepared by the method can prevent acid from losing in filtration, is environment-friendly and non-corrosive, and has high anti-scaling performance which reaches 90-99%; the bovine serum albumin filter has good filtering and separating performance, has the retention rate of more than 95 percent on bovine serum albumin, can stably exist in air and water, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of organic hybrid separation, and particularly relates to an acid-catalyzed COF self-assembled modified ultrafiltration membrane, and a preparation method and application thereof.
Background
Acid-doped ultrafiltration membranes, particularly polymeric acid-doped ultrafiltration membranes, known for use as anti-fouling membranes, can be made by a variety of processes. Ma Wenjing provides a method for purifying water by using a polyacrylic acid (PAA)/tungsten oxide/polyacrylonitrile (PP/WO3/PAN) composite membrane, which can realize heavy metal treatment, oil-water separation, scale resistance and the like. Patent CN 101007241a discloses a preparation process of polyacrylic acid/cellulose acetate (PAA/CA) composite membrane, in the preparation of PAA/CA Pervaporation (PV) composite membrane, due to the crosslinking action of glycol and aluminum nitrate to PAA and the thermal crosslinking of PAA completed by temperature programming, the problems of membrane stability in aqueous solution, preferential water permeability to ester-water mixture, mechanical strength and the like are solved. Patent CN 107081079A discloses a preparation method and application of an efficient hydrophilization modified anti-pollution polyether sulfone membrane, which synthesizes a hydrophilic block polymer by initiating a reversible addition fragmentation chain transfer polymerization (RAFT) method on the surface, and then physically blends the hydrophilic block polymer with polyether sulfone to prepare a PES/PAA-F127-PAA membrane. However, the existing acid modified ultrafiltration membrane is easy to run off in application and is a problem to be solved in water treatment of membrane materials.
COF is an Organic Framework material (solvent Organic Framework) and is a crystalline porous material with a periodic network structure formed by Covalent bonds of organisms. The method has the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity and tailorability of topological structures and the like. The invention provides an acid-catalyzed COF self-assembled modified ultrafiltration membrane, which realizes that acid is used as a COF catalyst and a modifier of the membrane, and COF porosity is utilized to prevent the acid from losing from the membrane, but no related literature discloses the preparation process at present.
Disclosure of Invention
The invention aims to provide an acid-catalyzed COF self-assembled modified ultrafiltration membrane and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the acid-catalyzed COF self-assembled modified ultrafiltration membrane comprises the following steps:
(1) dissolving polymer acid, a membrane substrate and polyvinylpyrrolidone (PVP) in an organic solvent to prepare a homogeneous solution;
(2) putting aldehydes and amines in a certain proportion into the homogeneous solution prepared in the step (1) in sequence, and stirring for reaction to prepare uniform and stable coating liquid;
(3) and (3) standing the coating liquid obtained in the step (2), performing ultrasonic defoaming treatment, performing film casting, and finally preparing the required ultrafiltration membrane by a non-solvent induced phase separation method.
In the step (1), the mass ratio of the polymer acid to the membrane substrate to the PVP is 0.001:1:0.03-0.1:1: 0.03; wherein the polymer acid is polylactic acid, polyacrylic acid, polymethacrylic acid and the like; the membrane substrate is any one of polyvinylidene fluoride (PVDF), Polyethylene (PE), polyether sulfone resin (PES) and Polysulfone (PSF).
The mass ratio of the film substrate used in the step (1) to the organic solvent is 1: 10-3: 10; the organic solvent is dimethylacetamide, dimethylformamide or N-methylpyrrolidone.
The temperature for preparing the homogeneous solution in the step (1) is 0-150 ℃.
The dosage of the aldehydes and the amines used in the step (2) is converted according to the molar ratio of the aldehyde groups to the amine groups of 0.5:1-2: 1; wherein the aldehydes are dialdehydes, trialdehydes or tetraaldehydes, and the amines are diamines or triamines.
The ratio of the total mass of the aldehydes and amines used in the step (2) to the mass of the film substrate is 0.1:100 to 5: 100.
The reaction temperature in the step (2) is 0-100 ℃, and the reaction time is 2min-48 h.
And (4) in the step (3), the temperature of the casting film is 20-100 ℃, and the time is 5-24 hours.
The invention has the following remarkable advantages:
according to the invention, the polymer acid is simultaneously used as the COF catalyst and the membrane modifier, and when the acid-doped ultrafiltration membrane is prepared, the COF formed by self-assembly has the porous characteristic, so that the acid is prevented from flowing off from the membrane, the obtained ultrafiltration membrane can stably exist in air and water, and the prepared ultrafiltration membrane has excellent anti-fouling performance and separation performance, is environment-friendly and has no corrosion. The experimental results show that: the ultrafiltration membrane prepared by the method has the anti-fouling performance of 90-99.9% on model molecules, the retention rate of more than 95% on bovine serum albumin, and the water flux of 80-140L/m2∙ h, hasHas good application prospect.
Drawings
FIG. 1 is a comparison of the surface topography of a pure PVDF ultrafiltration membrane (a) and a polyacrylic acid-modified PVDF ultrafiltration membrane (b) obtained in example 1;
FIG. 2 is a comparison graph of IR spectra of a pure PVDF ultrafiltration membrane, a polyacrylic acid doped PVDF ultrafiltration membrane obtained in comparative example 1, and a polyacrylic acid modified PVDF ultrafiltration membrane obtained in example 1;
FIG. 3 is a comparison of the surface topography of a pure PVDF ultrafiltration membrane (a) and an acetic acid modified PVDF ultrafiltration membrane (b) obtained in comparative example 2;
FIG. 4 is a comparison graph of IR spectra of a pure PVDF ultrafiltration membrane and an acetic acid modified PVDF ultrafiltration membrane obtained in comparative example 2.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
The preparation method of the acid-catalyzed COF self-assembled modified ultrafiltration membrane comprises the following steps:
(1) respectively putting 0.3g of polyacrylic acid, 0.3g of PVP and 10g of PVDF into 50ml of dimethylacetamide, and stirring at 60 ℃ to obtain homogeneous solutions;
(2) adding 0.05g of trimesic aldehyde and 0.03g of benzidine into the homogeneous solution, stirring at room temperature for reaction overnight, and preparing uniform and stable coating liquid;
(3) and standing the obtained coating liquid, performing ultrasonic defoaming treatment, scraping a film on a clean glass plate by using a scraper, standing for 2 minutes, putting the glass plate into deionized water for phase inversion, and soaking in the deionized water to remove residual solvent after the phase inversion is complete to obtain the ultrafiltration membrane.
Example 2
The preparation method of the acid-catalyzed COF self-assembled modified ultrafiltration membrane comprises the following steps:
(1) respectively putting 0.3g of polylactic acid, 0.3g of PVP and 10g of PVDF into 50ml of dimethylacetamide, and stirring at 60 ℃ to obtain homogeneous solution;
(2) adding 0.05g of mesitylene triformol and 0.03g of benzidine into the homogeneous solution, stirring at room temperature for reacting overnight to prepare uniform and stable coating liquid;
(3) and standing the obtained coating liquid, performing ultrasonic defoaming treatment, scraping a film on a clean glass plate by using a scraper, placing the glass plate in deionized water for phase inversion after placing for 2 minutes, and soaking the glass plate in the deionized water to remove residual solvent after the phase inversion is complete to obtain the ultrafiltration membrane.
Comparative example 1
(1) Respectively putting 0.3g of PVP and 10g of PVDF into 50ml of dimethylacetamide, and stirring at 60 ℃ to obtain homogeneous solution;
(2) adding 0.05g of trimesic aldehyde and 0.03g of benzidine into the homogeneous solution, and stirring 0.3g of polyacrylic acid at room temperature for reaction overnight to prepare uniform and stable coating liquid;
(3) and standing the obtained coating liquid, performing ultrasonic defoaming treatment, scraping a film on a clean glass plate by using a scraper, placing the glass plate in deionized water for phase inversion after placing for 2 minutes, and soaking the glass plate in the deionized water to remove residual solvent after the phase inversion is complete to obtain the ultrafiltration membrane.
Comparative example 2
(1) Respectively putting 0.1g of acetic acid, 0.3g of PVP and 10g of PVDF into 50ml of dimethylacetamide, and stirring at 60 ℃ to obtain homogeneous solutions;
(2) adding 0.05g of trimesic aldehyde and 0.03g of benzidine into the homogeneous solution, stirring at room temperature for reaction overnight, and preparing uniform and stable coating liquid;
(3) and standing the obtained coating liquid, performing ultrasonic defoaming treatment, scraping a film on a clean glass plate by using a scraper, placing the glass plate in deionized water for phase inversion after placing for 2 minutes, and soaking the glass plate in the deionized water to remove residual solvent after the phase inversion is complete to obtain the ultrafiltration membrane.
1. And (3) membrane flux test: the obtained sample film was evaluated at room temperature using a low-pressure film flux tester, and the film was placed in the testerThe area (A) is about 8 cm2. Prepressing for 30 min under the pressure of 0.1 MPa until the water flux is stable, measuring the water flux of the membrane, and repeating the three times to obtain an average value.
2. And (3) testing the retention rate: prepressing with 0.5 g/l BSA solution under 0.1 MPa for 10 min, collecting the penetrating fluid after it is stable, measuring its corresponding concentration with ultraviolet spectrophotometer, and calculating its retention rate.
3. Anti-fouling performance test with BSA as contaminant: introducing deionized water at room temperature under 0.1 MPa, pre-pressing for 30 min, and measuring pure water flux J after it is stable1Then, the deionized water in the wide-mouth bottle is changed into 0.5 g/l BSA solution to pollute the membrane for 30 min, then the membrane is taken out and washed by the deionized water for 10-15 min, then the BSA solution is changed into the deionized water, and after the BSA solution is stabilized for 30 min, the pure water flux J of the membrane is testedwnAnd the scale resistance was calculated according to the following formula:
TABLE 1
It can be seen from the comparison between example 1 and comparative example 1 that, the use of polyacrylic acid in situ catalysis of COF self-assembly in a solution of PVDF to prepare a casting solution can bind polymer acid on a PVDF membrane by using a synthesized COF, so that the water flux of the membrane is increased by about 20%, the anti-scaling recovery rate is increased by 10%, and after the membrane is soaked in water for one month, compared with the PVDF membrane directly doped with polymer acid, the water flux is only reduced by 10%, and the anti-scaling performance is not obviously changed.
As can be seen from the comparison of example 1 with comparative example 2, the water flux of the membrane prepared by using the polyacrylic acid catalyzed COF self-assembly is increased to 140L/m2Marked as h, which is significantly higher than that of the ultrafiltration membrane prepared by catalysis of acetic acid, the anti-fouling recovery rate of 0.5% BSA is increased to 92%, which is equivalent to that of the ultrafiltration membrane prepared by catalysis of acetic acid.
While there have been shown and described what are at present considered the fundamental principles of the invention and its essential features and advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present specification describes embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and it is to be understood that all embodiments may be combined as appropriate by one of ordinary skill in the art to form other embodiments as will be apparent to those of skill in the art from the description herein.
Claims (4)
1. A preparation method of an acid-catalyzed COF self-assembled modified ultrafiltration membrane is characterized by comprising the following steps:
(1) dissolving polymer acid, a membrane substrate and PVP in an organic solvent to prepare a homogeneous solution;
(2) putting aldehydes and amines in a certain proportion into the homogeneous solution prepared in the step (1) in sequence, and stirring for reaction to prepare uniform and stable coating liquid;
(3) standing the coating liquid obtained in the step (2), performing ultrasonic defoaming treatment, performing film casting, and finally preparing the required ultrafiltration membrane by a non-solvent induced phase separation method;
the mass ratio of the polymer acid, the membrane substrate and the PVP used in the step (1) is 0.03:1: 0.03; the polymer acid is polyacrylic acid or polylactic acid; the mass ratio of the used film substrate to the organic solvent is 1: 10-3: 10; the temperature for preparing homogeneous solution is 60 ℃;
the usage amount of the aldehyde and the amine used in the step (2) is converted according to the molar ratio of the aldehyde group to the amino group of 0.5:1-2:1, and the ratio of the total mass of the aldehyde and the amine to the mass of the film substrate is 0.8: 100; the aldehydes are trimesic aldehyde, and the amines are benzidine; the temperature of the stirring reaction is room temperature, and the stirring reaction is carried out overnight.
2. The method of preparing the acid-catalyzed COF self-assembled modified ultrafiltration membrane according to claim 1, wherein the membrane substrate in the step (1) is any one of PVDF, PE, PEs, and PSF.
3. The method of preparing the acid-catalyzed COF self-assembled modified ultrafiltration membrane of claim 1, wherein the organic solvent in step (1) is dimethylacetamide, dimethylformamide, or N-methylpyrrolidone.
4. An acid-catalyzed COF self-assembled modified ultrafiltration membrane made according to the method of any one of claims 1-3.
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