CN112316752B - Sulfonamide micromolecule surface modified polyamide composite membrane and preparation method thereof - Google Patents
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Abstract
The invention provides a sulfonamide micromolecule surface modified polyamide composite membrane and a preparation method thereof, wherein the polyamide composite membrane comprises an ultrafiltration basement membrane and a micromolecule modified polyamide layer, and the polyamide layer covers the surface of the ultrafiltration basement membrane; the functional groups of the micromolecules are amino and sulfonamide. According to the sulfonamide micromolecule surface modified polyamide composite membrane, the functional micromolecule monomer with amino and sulfonamide functional groups, which is easy to obtain, is grafted to the surface of the polyamide composite membrane through a secondary interface polymerization method to obtain the modified membrane, the hydrophilicity of the sulfonamide group is utilized to improve the hydrophilicity of the membrane surface, so that the mass transfer of water molecules is accelerated, the purposes of high flux and pollution resistance are realized, and on the premise of keeping high rejection rate, the water flux of the modified membrane can be improved by 38-65% compared with that of the unmodified polyamide membrane; in addition, the existence of the sulfonamide group provides more active N-chloridized group, thereby improving the capability of resisting active chlorine of the polyamide composite membrane.
Description
Technical Field
The invention belongs to the field of preparation of separation membranes, and particularly relates to a sulfonamide micromolecule surface modified polyamide composite membrane and a preparation method thereof.
Background
As an efficient and energy-saving green separation technology, the reverse osmosis technology is widely applied to the fields of seawater and brackish water desalination, wastewater treatment, biological product separation, environmental engineering, food, medicine and the like. Reverse osmosis polyamide composite membranes are generally composed of a porous support layer and a dense separation skin layer, wherein the dense separation skin layer is produced by interfacial polymerization of a polyamine with a polyacyl chloride. Compared with other reverse osmosis membranes, the membrane has the advantages of higher permeation flux, good selective separation performance and the like.
Despite the numerous advantages of reverse osmosis polyamide composite membranes, there still remains a problem to be solved that its permeation flux is still low compared to other membrane separation techniques, and cannot sufficiently satisfy the use in large areas; pollutants such as organic matters, colloidal particles and the like are inevitably present in the feed liquid, and the pollutants are combined on the surface of the membrane due to electrostatic interaction and hydrophobicity, so that the water flux and the salt rejection rate of the membrane are reduced sharply along with the extension of the operation time, and the operation cost is increased; in order to reduce membrane pollution, active chlorine is usually added into the feed liquid, but the increase of the active chlorine can degrade a polyamide layer, destroy the membrane structure, reduce the rejection rate of the membrane, and fail to obtain ideal aquatic products. Therefore, how to increase the permeation flux of the membrane and simultaneously increase the chlorine resistance of the membrane on the premise of keeping high retention rate is a problem which needs to be solved urgently at present.
Research shows that the material containing hydrophilic groups improves the hydrophilicity of the surface of the membrane so as to improve the anti-pollution capability of the membrane; the introduction of the sacrificial group which can react with active chlorine can improve the chlorine resistance of the membrane and prolong the service life of the membrane. The sulfonamide group is used as a hydrophilic group, and is combined with water molecules through electrostatic force and hydrogen bonds, so that the transmission capability of water on the surface of the membrane is improved; meanwhile, the sulfonamide group can be combined with active chlorine to avoid a large amount of contact between the active chlorine and polyamide, and the sulfonamide group can be recovered after simple alkali washing, so that the adaptability of the membrane in a severe environment is improved. Therefore, the use of a material having a sulfonamide group makes it possible to produce a membrane product having good water permeability, anti-contamination property and chlorine resistance. According to the invention, amino is combined with acyl chloride groups on the surface of the membrane through surface secondary interfacial polymerization, so that small molecular monomers with sulfonamide groups are introduced to the surface of the polyamide composite membrane, and the surface-modified polyamide composite membrane is obtained. The sulfonamide group endows the membrane surface with high hydrophilicity and improved high flux, and takes into account the improved chlorine resistance, so that one functional group realizes three purposes, and the range is widened for the practical application.
Disclosure of Invention
In view of the above, the present invention aims to overcome the defects in the prior art, and provides a sulfonamide small-molecule surface modified polyamide composite membrane and a preparation method thereof, so as to improve the permeation flux, the contamination resistance and the chlorine resistance of the membrane. The preparation method has the advantages of simple operation, easy large-scale production and the like, effectively improves the water flux, pollution resistance and chlorine resistance of the polyamide composite membrane under the condition of maintaining higher composite membrane interception performance, and widens the application range of the reverse osmosis polyamide composite membrane.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a sulfonamide micromolecule surface modified polyamide composite membrane comprises an ultrafiltration basement membrane and a polyamide layer modified by micromolecules, wherein the nascent state polyamide layer is soaked in an aqueous solution containing amino and sulfonamide group molecules, then the redundant aqueous solution is removed, and the polyamide composite membrane is dried and washed to obtain a reverse osmosis polyamide composite membrane with high flux, pollution resistance and chlorine resistance, and the polyamide layer covers the surface of the ultrafiltration basement membrane; the functional groups of the small molecules comprise amino and sulfonamide groups.
Further, the small molecule is at least one of sulfanilamide, sulfanilamide or 2-aminoethyl sulfonamide hydrochloride; preferably, the small molecule is at least one of sulfanilamide or 2-aminoethyl sulfonamide hydrochloride.
The molecular formula of the sulfanilamide is as follows:
the molecular formula of the m-aminobenzenesulfonamide is as follows:
the molecular formula of the 2-aminoethylsulfamide hydrochloride is as follows:
furthermore, the ultrafiltration basement membrane is a polysulfone ultrafiltration membrane.
Furthermore, the sulfanilamide, the m-sulfanilamide or the 2-aminoethyl sulfonamide hydrochloride is a product produced in industrial quantity.
The preparation method of the sulfonamide micromolecule surface modified polyamide composite membrane comprises the following steps:
(1) immersing the ultrafiltration basement membrane in the polyamine aqueous phase solution for 1-5min, and then taking out and removing the polyamine aqueous phase solution on the surface;
(2) immersing the ultrafiltration basement membrane treated in the step (1) in an organic phase solution for 1-3min, then taking out and removing the organic phase solution on the surface, and washing the surface of the membrane by using an organic solvent;
(3) and (3) drying the surface of the ultrafiltration basement membrane treated in the step (2), soaking the ultrafiltration basement membrane in the aqueous phase solution for 2-10min, taking out and removing the aqueous phase solution on the surface, washing the ultrafiltration basement membrane with deionized water, and performing thermal crosslinking to obtain the sulfonamide micromolecule surface modified reverse osmosis polyamide composite membrane.
Further, the polyamine aqueous phase solution in the step (1) is one of piperazine or m-phenylenediamine; preferably, the aqueous solution of polyamine in the step (1) is piperazine, and the concentration of the piperazine is 0.2-1.0 wt%; preferably, the aqueous solution of polyamine in the step (1) is m-phenylenediamine, and the concentration of the m-phenylenediamine is 1.0 to 3.4 wt%.
The aqueous piperazine solution comprises 0.2-1.0 wt% of piperazine and 0.2-1.0 wt% of sodium phosphate. The aqueous solution of m-phenylenediamine is 1.0-3.4 wt% of m-phenylenediamine, 1.2-2.4 wt% of camphorsulfonic acid and 0.5-1.1 wt% of triethylamine.
Further, the organic phase solution in the step (2) contains aromatic polybasic acyl chloride, and the concentration of the aromatic polybasic acyl chloride is 0.05-0.15 wt%; the aromatic polybasic acyl chloride is trimesoyl chloride; the solvent of the organic phase solution is n-hexane.
Further, the pH value of the aqueous phase solution in the step (3) is 7-11; the temperature of the aqueous phase solution in the step (3) is 5-25 ℃; the aqueous phase solution in the step (3) contains small molecules, and the concentration of the small molecules is 0.1-2 wt%; the small molecule is at least one of sulfanilamide, m-sulfanilamide or 2-aminoethyl sulfonamide hydrochloride; preferably, the small molecule is at least one of sulfanilamide or 2-aminoethyl sulfonamide hydrochloride.
Further, the temperature of the thermal crosslinking step in the step (3) is 45-80 ℃, and the reaction time is 2-10 min.
An application of a sulfonamide micromolecule surface modified polyamide composite membrane in preparing a polyamide composite reverse osmosis membrane and a polyamide composite nanofiltration membrane.
Compared with the prior art, the invention has the beneficial effects that:
(1) the sulfonamide micromolecule surface modified polyamide composite membrane provided by the invention grafts the functional micromolecule monomer with amino and sulfonamide groups onto the surface of the polyamide composite membrane through a surface secondary interface polymerization method, the method is simpler, the used sulfonamide micromolecules are industrial mass products, the cost is lower, and the defects of complex chemical synthesis process, high cost and the like in a laboratory are overcome. The method is easy to scale, and can effectively improve the water flux, the pollution resistance and the chlorine resistance of the reverse osmosis polyamide composite membrane.
(2) The sulfonamide micromolecule surface modified polyamide composite membrane increases the hydrophilicity of the membrane surface, greatly improves the mass transfer rate of water molecules, obviously improves the water flux of the membrane, improves the water flux of the modified membrane by 38-65% compared with the flux of an unmodified polyamide membrane, simultaneously keeps the retention rate of the membrane above 99%, can react with sulfonamide groups in preference to active chlorine, reduces the damage of the active chlorine to a polyamide separation layer, and improves the chlorine resistance of the polyamide composite membrane.
(3) According to the sulfonamide micromolecule surface modified polyamide composite membrane, functional micromolecules are used as post-modification materials, the surface roughness of the prepared polyamide composite membrane is obviously reduced, the membrane surface is smoother, the adhesion of pollutants is reduced, and the anti-pollution capacity of the membrane surface is improved to a certain extent.
(4) The sulfonamide micromolecule surface modified polyamide composite membrane adopts the functional sulfonamide group to improve the surface hydrophilicity of the membrane and enhance the negative charge of the surface of the membrane, so that the pollution resistance of the modified membrane to pollutants with negative charge is increased, and meanwhile, the pollution resistance of the modified membrane to pollutants with positive charge is better than that of the original aromatic polyamide composite reverse osmosis membrane due to the smooth surface and better hydrophilicity of the modified membrane.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention.
In the drawings:
FIG. 1 is a graph showing the results of water flux and salt rejection tests on modified and original aromatic polyamide composite reverse osmosis membranes according to examples 1 and 4 of the present invention and comparative examples;
FIG. 2 is a microscopic topography of the surface of modified and initial aromatic polyamide composite reverse osmosis membranes prepared in examples 1 and 4 of the present invention and comparative examples: a is a comparative example, B is example 1, C is example 4;
FIG. 3 is a result of a water contact angle test of the surface of a modified and original aromatic polyamide composite reverse osmosis membrane according to examples 1 and 4 of the present invention and a comparative example;
FIG. 4 shows the results of the measurement of the electrification characteristics of the surfaces of the modified and original aromatic polyamide composite reverse osmosis membranes obtained in examples 1 and 4 of the present invention and comparative examples;
FIG. 5 is a graph showing the flux change (concentration: 0.3g/L) of the modified and original aromatic polyamide composite reverse osmosis membranes obtained in examples 1 and 4 of the present invention and comparative example: a is a filtered bovine serum albumin aqueous solution, B is a filtered sodium alginate aqueous solution, and C is a filtered humic acid aqueous solution;
FIG. 6 shows the results of a chlorine resistance test (NaClO concentration of 500ppm) of modified and original aromatic polyamide composite reverse osmosis membranes obtained in example 4 of the present invention and comparative example.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
The evaluation of the osmotic selectivity and the anti-pollution performance of the polyamide composite reverse osmosis membrane is tested by adopting a cross-flow reverse osmosis experimental device, and the test conditions are as follows: the temperature is 25 ℃, the pressure is 1.5MPa, and the effective membrane area is 28.26cm2The concentration of the NaCl solution of the feeding liquid is 2.0g/L, and bovine serum albumin, sodium alginate and humic acid (the concentration is 0.3g/L) are respectively used as model pollutants.
Example 1
A sulfanilamide micromolecule modified surface polyamide composite membrane comprises an ultrafiltration basement membrane and a micromolecule modified polyamide layer, wherein the polyamide layer covers the surface of the ultrafiltration basement membrane;
the small molecule is sulfanilamide.
The preparation method of the sulfanilamide micromolecule modified surface polyamide composite membrane comprises the following steps:
(1) immersing a polysulfone ultrafiltration membrane in a mixed aqueous phase solution containing 2.4 wt% of camphorsulfonic acid, 1.1 wt% of triethylamine and 2.0 wt% of m-phenylenediamine for 2min, and then taking out and removing the aqueous phase solution on the surface;
(2) immersing the polysulfone ultrafiltration membrane treated in the step (1) in a normal hexane solution containing 0.1 wt% of trimesoyl chloride for 1min, then taking out and removing the organic phase solution on the surface, and washing the surface of the membrane by using normal hexane;
(3) and (3) airing the surface of the polysulfone ultrafiltration membrane treated in the step (2), soaking the polysulfone ultrafiltration membrane in 0.5 wt% of sulfanilamide aqueous solution (pH is 11 and temperature is 5 ℃) for 2min, taking out and removing the aqueous phase solution on the surface, and thermally crosslinking at 60 ℃ for 10min to obtain the sulfonamide micromolecule surface modified polyamide composite reverse osmosis membrane.
Example 2
A sulfanilamide micromolecule modified surface polyamide composite membrane comprises an ultrafiltration basement membrane and a micromolecule modified polyamide layer, wherein the polyamide layer covers the surface of the ultrafiltration basement membrane;
the small molecule is sulfanilamide.
The preparation method of the sulfanilamide micromolecule modified surface polyamide composite membrane comprises the following steps:
(1) immersing a polysulfone ultrafiltration membrane in a mixed aqueous phase solution containing 2.4 wt% of camphorsulfonic acid, 1.1 wt% of triethylamine and 2.0 wt% of m-phenylenediamine for 2min, and then taking out and removing the aqueous phase solution on the surface;
(2) immersing the polysulfone ultrafiltration membrane treated in the step (1) in a normal hexane solution containing 0.1 wt% of trimesoyl chloride for 1min, then taking out and removing the organic phase solution on the surface, and washing the surface of the membrane by using normal hexane;
(3) and (3) airing the surface of the polysulfone ultrafiltration membrane treated in the step (2), soaking the polysulfone ultrafiltration membrane in 0.5 wt% of sulfanilamide aqueous solution (the pH is 11 and the temperature is 25 ℃) for 10min, taking out and removing the aqueous phase solution on the surface, and thermally crosslinking the surface at 60 ℃ for 10min to obtain the sulfonamide micromolecule surface modified polyamide composite reverse osmosis membrane.
Example 3
A sulfanilamide micromolecule modified surface polyamide composite membrane comprises an ultrafiltration basement membrane and a micromolecule modified polyamide layer, wherein the polyamide layer covers the surface of the ultrafiltration basement membrane;
the small molecule is m-aminobenzene sulfonamide.
The preparation method of the sulfanilamide micromolecule modified surface polyamide composite membrane comprises the following steps:
(1) immersing a polysulfone ultrafiltration membrane in a mixed aqueous phase solution containing 2.4 wt% of camphorsulfonic acid, 1.1 wt% of triethylamine and 2.0 wt% of m-phenylenediamine for 2min, and then taking out and removing the aqueous phase solution on the surface;
(2) immersing the polysulfone ultrafiltration membrane treated in the step (1) in a normal hexane solution containing 0.1 wt% of trimesoyl chloride for 1min, then taking out and removing the organic phase solution on the surface, and washing the surface of the membrane by using normal hexane;
(3) and (3) airing the surface of the polysulfone ultrafiltration membrane treated in the step (2), soaking the polysulfone ultrafiltration membrane in 0.5 wt% of m-aminobenzenesulfonamide aqueous solution (the pH is 11 and the temperature is 25 ℃) for 2min, taking out and removing the aqueous phase solution on the surface, and thermally crosslinking at 60 ℃ for 10min to obtain the sulfonamide micromolecule modified surface polyamide composite reverse osmosis membrane.
Example 4
A sulfanilamide micromolecule modified surface polyamide composite membrane comprises an ultrafiltration basement membrane and a micromolecule modified polyamide layer, wherein the polyamide layer covers the surface of the ultrafiltration basement membrane;
the small molecule is 2-aminoethyl sulfonamide hydrochloride.
The preparation method of the sulfanilamide micromolecule modified surface polyamide composite membrane comprises the following steps:
(1) immersing a polysulfone ultrafiltration membrane in a mixed aqueous phase solution containing 2.4 wt% of camphorsulfonic acid, 1.1 wt% of triethylamine and 2.0 wt% of m-phenylenediamine for 2min, and then taking out and removing the aqueous phase solution on the surface;
(2) immersing the polysulfone ultrafiltration membrane treated in the step (1) in a normal hexane solution containing 0.1 wt% of trimesoyl chloride for 1min, then taking out and removing the organic phase solution on the surface, and washing the surface of the membrane by using normal hexane;
(3) and (3) airing the surface of the polysulfone ultrafiltration membrane treated in the step (2), soaking the polysulfone ultrafiltration membrane in 0.5 wt% of m-aminobenzenesulfonamide aqueous solution (the pH is 11 and the temperature is 5 ℃) for 2min, taking out and removing the aqueous phase solution on the surface, and thermally crosslinking at 60 ℃ for 10min to obtain the sulfonamide micromolecule modified surface polyamide composite reverse osmosis membrane.
Example 5
A sulfanilamide micromolecule modified surface polyamide composite membrane comprises an ultrafiltration basement membrane and a micromolecule modified polyamide layer, wherein the polyamide layer covers the surface of the ultrafiltration basement membrane;
the small molecule is 2-aminoethyl sulfonamide hydrochloride.
The preparation method of the sulfanilamide micromolecule modified surface polyamide composite membrane comprises the following steps:
(1) immersing a polysulfone ultrafiltration membrane in a mixed aqueous phase solution containing 2.4 wt% of camphorsulfonic acid, 1.1 wt% of triethylamine and 2.0 wt% of m-phenylenediamine for 2min, and then taking out and removing the aqueous phase solution on the surface;
(2) immersing the polysulfone ultrafiltration membrane treated in the step (1) in a normal hexane solution containing 0.1 wt% of trimesoyl chloride for 1min, then taking out and removing the organic phase solution on the surface, and washing the surface of the membrane by using normal hexane;
(3) and (3) airing the surface of the polysulfone ultrafiltration membrane treated in the step (2), soaking the surface of the polysulfone ultrafiltration membrane in 0.5 wt% of 2-aminoethyl sulfonamide hydrochloride aqueous solution (with the pH value of 11 and the temperature of 25 ℃) for 10min, taking out and removing the aqueous phase solution on the surface, and thermally crosslinking the aqueous phase solution at the temperature of 60 ℃ for 10min to obtain the sulfonamide micromolecule modified surface polyamide composite reverse osmosis membrane.
Comparative example
A polyamide composite reverse osmosis membrane is a polysulfone ultrafiltration membrane with a polyamide layer covered on the surface;
the preparation method of the polyamide composite reverse osmosis membrane comprises the following steps:
(1) immersing a polysulfone ultrafiltration membrane in a mixed aqueous phase solution containing 2.4 wt% of camphorsulfonic acid, 1.1 wt% of triethylamine and 2.0 wt% of m-phenylenediamine for 2min, and then taking out and removing the aqueous phase solution on the surface;
(2) immersing the polysulfone ultrafiltration membrane treated in the step (1) in a normal hexane solution containing 0.1 wt% of trimesoyl chloride for 1min, then taking out and removing the organic phase solution on the surface, and washing the surface of the membrane by using normal hexane;
(3) and (3) drying the surface of the polysulfone ultrafiltration membrane treated in the step (2), and then carrying out heat crosslinking for 10min at the temperature of 60 ℃ to obtain the comparative polyamide composite reverse osmosis membrane.
The separation performance of the polyamide composite reverse osmosis membrane was measured for examples 1 to 5 and comparative example, and the results are shown in table 1.
TABLE 1 separation Performance of Polyamide composite reverse osmosis Membrane
The results of examples 1-5 and comparative example show that the polyamide composite reverse osmosis membrane after surface modification of small molecules of sulfonamides has a higher water flux while maintaining a high rejection rate as shown in fig. 1, compared to the original polyamide composite reverse osmosis membrane.
The microscopic topography maps of the surfaces of the modified and initial aromatic polyamide composite reverse osmosis membranes prepared in the examples 1 and 4 and the comparative example are observed, as shown in fig. 2, it can be seen that the surface topography of the membranes before and after modification is obviously flattened, which shows that the surface topography of the membranes can be improved by the modification of the small sulfanilamide molecules;
the water contact angle test is carried out on the surfaces of the modified and original aromatic polyamide composite reverse osmosis membranes prepared in the examples 1, 4 and the comparative example, and the water contact angle is reduced from 75.49 degrees to 48.49 degrees before and after the surface modification of the sulfonamide micromolecules as shown in figure 3;
the surface of the modified and original aromatic polyamide composite reverse osmosis membrane prepared in example 1, example 4 and comparative example is subjected to a charging test, and as shown in fig. 4, after the surface of the membrane is modified by sulfonamide small molecules, the electronegativity of the membrane surface is reduced, because the electronegative acyl chloride groups on the membrane surface are replaced by sulfonamide groups;
measuring the flux change (the concentration is 0.3g/L) of the modified and original aromatic polyamide composite reverse osmosis membranes prepared in the embodiment 1, the embodiment 4 and the comparative example 1 for filtering bovine serum albumin aqueous solution, sodium alginate aqueous solution and humic acid aqueous solution, as shown in FIG. 5, compared with the original polyamide composite reverse osmosis membrane, the flux attenuation rate of the modified polyamide composite reverse osmosis membrane with the surface modified by the small sulfanilamide molecules is obviously reduced, the flux recovery rate is obviously higher after simple cleaning, and the pollution resistance is obviously enhanced;
chlorine resistance (concentration of NaClO is 500ppm) of the modified and original aromatic polyamide composite reverse osmosis membranes prepared in example 4 and the comparative examples was measured, and as shown in FIG. 6, after surface modification with small sulfanilamide molecules, the chlorine resistance of the modified membrane was significantly increased, and the membrane performance was more stable.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (12)
1. A polyamide composite membrane with modified sulfonamide micromolecule surface is characterized in that: the polyamide composite membrane comprises a porous basement membrane and a polyamide layer modified by small sulfanilamide molecules, wherein the polyamide layer modified by the small sulfanilamide molecules is prepared by a surface secondary interface polymerization method; the polyamide layer covers the surface of the porous basement membrane; the sulfonamide micromolecules contain two functional groups, namely amino and sulfonamide;
the sulfanilamide small molecule is at least one of sulfanilamide, m-sulfanilamide or 2-aminoethyl sulfonamide hydrochloride.
2. The sulfonamide small-molecule surface-modified polyamide composite membrane according to claim 1, characterized in that: the sulfanilamide small molecule is at least one of sulfanilamide or 2-aminoethyl sulfonamide hydrochloride.
3. The sulfonamide small-molecule surface-modified polyamide composite membrane according to claim 1, characterized in that: the porous basement membrane is an organic porous membrane, a ceramic porous membrane or a metal porous membrane, and the pore diameter range of the porous basement membrane is 5nm-500 nm.
4. The sulfonamide small-molecule surface-modified polyamide composite membrane according to claim 1, characterized in that: the aperture range of the porous basement membrane is between 10nm and 50 nm.
5. A preparation method of the sulfonamide small-molecule surface modified polyamide composite membrane as claimed in any one of claims 1 to 4, characterized in that: the method comprises the following steps:
(1) immersing the porous basement membrane in the polyamine aqueous phase solution for 10 seconds to 5 minutes, and then taking out and removing the polyamine aqueous phase solution on the surface of the membrane;
(2) immersing the porous base membrane treated in the step (1) in an acyl chloride organic phase solution for 10 seconds to 3 minutes, then taking out and removing the organic phase solution on the surface of the membrane, and washing the surface of the membrane by using an organic solvent;
(3) and (3) drying the surface of the porous basement membrane treated in the step (2), soaking the porous basement membrane in an aqueous phase solution containing sulfonamide micromolecules for 1-10 minutes, taking out and removing the excess aqueous phase solution on the surface, and then carrying out thermal crosslinking to obtain the sulfonamide micromolecule surface modified polyamide composite membrane.
6. The preparation method of the sulfonamide micromolecule surface modified polyamide composite membrane according to claim 5, which is characterized by comprising the following steps: the polyamine aqueous phase solution in the step (1) is one of piperazine or m-phenylenediamine.
7. The preparation method of the sulfonamide micromolecule surface modified polyamide composite membrane according to claim 5, which is characterized by comprising the following steps: the polyamine aqueous phase solution in the step (1) is piperazine, and the concentration of the piperazine is 0.2-1.0 wt%.
8. The preparation method of the sulfonamide micromolecule surface modified polyamide composite membrane according to claim 6, which is characterized by comprising the following steps: the polyamine aqueous phase solution in the step (1) is m-phenylenediamine, and the concentration of the m-phenylenediamine is 1.0-3.4 wt%.
9. The preparation method of the sulfonamide micromolecule surface modified polyamide composite membrane according to claim 5, which is characterized by comprising the following steps: the acyl chloride organic phase solution in the step (2) contains aromatic polybasic acyl chloride, and the concentration of the aromatic polybasic acyl chloride is 0.05-0.15 wt%; the aromatic polybasic acyl chloride is trimesoyl chloride; the solvent of the organic phase solution is n-hexane and isoparaffin Isopar G.
10. The preparation method of the sulfonamide micromolecule surface modified polyamide composite membrane according to claim 5, which is characterized by comprising the following steps: the pH value of the aqueous phase solution in the step (3) is 7-11; the temperature of the aqueous phase solution in the step (3) is 5-25 ℃; the aqueous phase solution in the step (3) contains sulfonamide micromolecules, and the concentration of the sulfonamide micromolecules is 0.1-2 wt%; the sulfanilamide small molecule is at least one of sulfanilamide, m-sulfanilamide or 2-aminoethyl sulfonamide hydrochloride.
11. The preparation method of the sulfonamide micromolecule surface modified polyamide composite membrane according to claim 5, which is characterized by comprising the following steps: the small molecule is at least one of sulfanilamide or 2-aminoethyl sulfonamide hydrochloride.
12. The preparation method of the sulfonamide micromolecule surface modified polyamide composite membrane according to claim 4, which is characterized by comprising the following steps: the thermal crosslinking temperature in the step (3) is 40-100 ℃, and the reaction time is 1-10 min.
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| CN112473398B (en) * | 2020-12-25 | 2022-12-27 | 湖南澳维膜科技有限公司 | High-desalination and anti-pollution reverse osmosis membrane and preparation method thereof |
| CN113230912B (en) * | 2021-04-29 | 2022-06-24 | 浙江理工大学 | Preparation method of chlorine-resistant composite nanofiltration membrane |
| CN114425238B (en) * | 2022-01-19 | 2022-11-25 | 自然资源部天津海水淡化与综合利用研究所 | Stain-resistant chlorine-resistant dual-functional polyamide composite reverse osmosis membrane and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102317350A (en) * | 2009-02-20 | 2012-01-11 | 国际商业机器公司 | PA membrane with fluorinated alcohols functionality |
| CN103648625A (en) * | 2012-05-31 | 2014-03-19 | Lg化学株式会社 | Highly permeable reverse osmosis membrane comprising carbodiimide-based compound, and method for preparing same |
| CN105435645A (en) * | 2014-07-22 | 2016-03-30 | 中国石油化工股份有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN105771672A (en) * | 2016-04-18 | 2016-07-20 | 天津工业大学 | Antipollution and antibacterial aromatic polyamide reverse osmosis composite membrane and preparation method |
| CN110665369A (en) * | 2019-08-01 | 2020-01-10 | 湖南大学 | Anti-pollution loose nanofiltration membrane with in-situ catalysis function and preparation method and application thereof |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4761234A (en) * | 1985-08-05 | 1988-08-02 | Toray Industries, Inc. | Interfacially synthesized reverse osmosis membrane |
| KR100863371B1 (en) * | 2000-05-23 | 2008-10-13 | 오스모닉스 인코포레이티드 | Polysulfonamide Matrices |
| CN101716471B (en) * | 2010-01-21 | 2012-10-10 | 天津大学 | Fluorizated cellulose acetate film and preparation method |
| CN102188912A (en) * | 2010-03-16 | 2011-09-21 | 武少禹 | Method for preparing chlorine-resistant polyamide reverse osmosis composite membrane |
| CN101829508A (en) * | 2010-05-11 | 2010-09-15 | 杭州水处理技术研究开发中心有限公司 | Novel polyamide nanofiltration membrane and preparation method thereof |
| CN102120149B (en) * | 2011-01-30 | 2014-03-12 | 杭州方然滤膜技术有限公司 | Method for preparing acid-proof polysulfonamide nanofiltration composite film |
| KR20140131810A (en) * | 2013-05-06 | 2014-11-14 | 삼성전자주식회사 | Semi-permeable film, membrane including the semi-permeable film,and method of manufacturing the semi-permeable film |
| CN103331110B (en) * | 2013-05-27 | 2015-03-04 | 天津工业大学 | Pollution-resistant chlorine polyamide-resistant reverse osmosis composite membrane and preparation method thereof |
| CN103463999B (en) * | 2013-09-06 | 2014-10-22 | 烟台绿水赋膜材料有限公司 | Preparation method of ultrathin salt-cutting separation membrane |
| CN105457509B (en) * | 2015-11-27 | 2018-04-20 | 浙江大学 | Reproducible polyamide reverse osmosis composite film of chlorine-resistant property and preparation method thereof |
| WO2018000361A1 (en) * | 2016-06-30 | 2018-01-04 | 中国石油大学(华东) | Preparation method for polysulfonamide nanofiltration or reverse osmosis composite membrane by molecular layer assembly |
| JP2018012089A (en) * | 2016-07-22 | 2018-01-25 | 富士フイルム株式会社 | Gas separation membrane, manufacturing method of gas separation membrane, gas separation membrane module and gas separator |
| CN108159891A (en) * | 2018-01-11 | 2018-06-15 | 中国石油大学(华东) | A kind of N- sulfenamides based polyamide water softens loose reverse osmosis composite membrane and preparation method thereof |
| EP3546510A1 (en) * | 2018-03-26 | 2019-10-02 | LANXESS Deutschland GmbH | Polyamide compositions |
| CN111686592A (en) * | 2019-03-11 | 2020-09-22 | 湖州欧美新材料有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN111558300B (en) * | 2020-04-07 | 2022-03-22 | 天津工业大学 | Micromolecular zwitterion modified surface polyamide composite membrane and preparation method thereof |
-
2020
- 2020-11-04 CN CN202011217264.4A patent/CN112316752B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102317350A (en) * | 2009-02-20 | 2012-01-11 | 国际商业机器公司 | PA membrane with fluorinated alcohols functionality |
| CN103648625A (en) * | 2012-05-31 | 2014-03-19 | Lg化学株式会社 | Highly permeable reverse osmosis membrane comprising carbodiimide-based compound, and method for preparing same |
| CN105435645A (en) * | 2014-07-22 | 2016-03-30 | 中国石油化工股份有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN105771672A (en) * | 2016-04-18 | 2016-07-20 | 天津工业大学 | Antipollution and antibacterial aromatic polyamide reverse osmosis composite membrane and preparation method |
| CN110665369A (en) * | 2019-08-01 | 2020-01-10 | 湖南大学 | Anti-pollution loose nanofiltration membrane with in-situ catalysis function and preparation method and application thereof |
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