CN115738743A - Method for preparing durable high-performance ultrafiltration membrane based on supermolecular assembly reinforced blending method - Google Patents
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- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 67
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A method for preparing a durable high-performance ultrafiltration membrane based on a supermolecule assembly reinforced blending method belongs to the technical field of ultrafiltration membrane preparation. The ultrafiltration membrane solves the problems of weak pollution resistance and poor long-term use stability of the conventional ultrafiltration membrane. The method comprises the following steps: mixing and stirring beta-cyclodextrin, pluronic F118, PES and DMAC, and defoaming to obtain a casting solution; and cooling the casting film liquid, casting, solidifying, taking down the film and cleaning. The invention regulates the enrichment degree of Pluronic118 on the surface of a membrane in a non-solvent induced phase inversion process and the loss of Pluronic118 in a use process based on the supermolecule assembly of beta-cyclodextrin. Along with the increase of the content of beta-cyclodextrin, the enrichment degree of Pluronic118 on the surface of the membrane is increased, and the loss degree of the Pluronic118 in long-term use is reduced, so that the problem of loss of a segregation modifier in the preparation and use processes of the ultrafiltration membrane is solved, and the surface hydrophilicity, the pollution resistance and the long-term use stability of the ultrafiltration membrane are improved.
Description
Technical Field
The invention belongs to the technical field of ultrafiltration membrane preparation, and particularly relates to a method for preparing a durable high-performance ultrafiltration membrane based on a supermolecular assembly reinforced blending method.
Background
Ultrafiltration has been a highly efficient, economical and safe membrane separation technique that has been attracting attention for a long time in the field of water treatment, and development of an ultrafiltration membrane having excellent performance has been a core problem in the development of ultrafiltration technology. At present, the non-solvent induced phase inversion technology is a method used for preparing most ultrafiltration membranes, however, in the ultrafiltration process, a large amount of impurities are gathered on the surface of the ultrafiltration membrane due to the interception function of membrane pores, and are easy to be adsorbed on the surface of the membrane or adhered to the inner walls of the membrane pores as pollutants, so that the problem of membrane pollution is caused. Along with the gradual increase of the pollution degree in the use process, the permeability of the membrane is greatly reduced, and further the problems of greatly reduced separation efficiency, increased operation energy consumption, shortened service life and the like are caused.
Compared with the surface grafting method, the blending method has the advantages of simple operation, mild conditions, no need of complex equipment, no by-products and low comprehensive cost. However, because there is no covalent interaction between the modifier and the membrane substrate, the modifier has insufficient stability and is present during membrane preparation and use. During membrane preparation, a portion of the modifier may be lost into the non-solvent bath as the non-solvent is exchanged with the solvent. When the membrane is used, the surface of the membrane is sheared to water flow to continuously flush the modifier, so that the modifier can be gradually pulled out of the membrane substrate and lost.
Through a great deal of research, amphiphilic block copolymers such as pluronic series are spotlighted in the field of blending modification of ultrafiltration membranes due to the special amphiphilic molecular structure. Compared to homopolymeric modifiers (polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), etc.) that have been successfully introduced into blending methods to date, copolymers of the pluronic series have a triblock structure of poly (ethylene oxide) -poly (ethylene oxide) (PEO-PPO-PEO). As a modifier, the porous silicon dioxide has the double functions of pore forming and surface modification. On one hand, the block modifier covering the solvent-non-solvent interface reduces the solvent-non-solvent interaction rate, delays the phase inversion process, is beneficial to forming more pores on the surface of the membrane, and obviously increases the porosity. On the other hand, the hydrophobic effect between the hydrophobic PPO group in the block modifier and the membrane substrate makes the block modifier tend to be anchored in the membrane substrate, and the long-term stability of modification is guaranteed; meanwhile, the hydrophilic PEO groups are induced and separated at a membrane-water interface, so that the membrane has good hydrophilicity. Thus, an amphiphilic block copolymer with hydrophobic group anchors and hydrophilic segments is an additive suitable for ultrafiltration membrane modification.
The cyclodextrin is a hollow truncated cone-shaped oligomer consisting of D- (+) -glucopyranose, and the outer wall and the small-mouth end are rich in hydroxyl and are strong in polarity; the inner wall and the large opening end do not contain hydroxyl and are in weak polarity. The high-polarity polymer easily enters the cyclodextrin cavity from the small-opening end, and the low-polarity polymer easily enters the cyclodextrin cavity from the large-opening end. In the environment of non-solvent and solvent, the weak polar chain segment of the modifier and the membrane main body polymer can be stably nested in the inner cavity of the cyclodextrin to form stable nodes. For the block copolymer with strong polarity at two ends and weak polarity in the middle, the cyclodextrin is hardly likely to fall off once nested to the weak polarity segment part. The cyclodextrin is widely applied to the pharmaceutical industry and the food industry due to the inclusion and coordination capacity, and has good economy and safety.
Disclosure of Invention
The invention aims to solve the problems of weak pollution resistance and poor long-term use stability of the conventional ultrafiltration membrane, and provides a method for preparing a durable high-performance ultrafiltration membrane based on a supermolecular assembly reinforced blending method.
A method for preparing a durable high-performance ultrafiltration membrane based on a supermolecule assembly strengthening blending method comprises the following steps:
1. mixing beta-cyclodextrin, pluronic F118, PES and DMAC, mechanically stirring for 20-26 h at 65-75 ℃, and defoaming to obtain a casting solution;
2. the casting solution is uniformly cast on a smooth polished fine glass plate after being cooled, and the membrane is taken down and cleaned after being solidified, thus completing the method for preparing the durable high-performance ultrafiltration membrane based on the supermolecular assembly reinforced blending method;
wherein the casting thickness of the casting solution in the second step is 240-260 μm.
Further, the dosage of the beta-cyclodextrin in the step one is as follows: 1wt%, 3wt%, 4wt%, 5wt% or 7wt% of the total amount of PES.
Further, the dosage of Pluronic F118 in the first step is as follows: accounting for 30wt percent to 40wt percent of the total weight of PES.
Further, the dosage of PES in the step one is as follows: accounting for 12wt percent to 18wt percent of the total weight of the casting solution.
Further, in the first step, PES is Pasteur 3000P in Germany, and has a relative molecular weight of 2X 10 4 ～5×10 5 。
Further, in step one, the relative molecular weight of Pluronic118 is 14600.
Further, in the first step, the defoaming: standing in 50 deg.C water bath for 4 hr.
Further, the casting solution in the second step is cooled to 23-27 ℃.
Further, the solidification in step two: placing the mixture in deionized water solution at the temperature of 22-27 ℃ for coagulation for 8-12 min.
Further, the cleaning in the step two: and washing with deionized water for 2-3 times.
Further, the prepared ultrafiltration membrane is stored in deionized water for at least 12 hours and then is used.
The invention has the advantages that: supramolecular assembly based on beta-cyclodextrin regulates the enrichment degree of Pluronic118 on the surface of a membrane in a non-solvent induced phase inversion process and the loss of Pluronic118 in a use process. Along with the increase of the content of beta-cyclodextrin, the enrichment degree of Pluronic118 on the surface of the membrane is increased, and the loss degree of the Pluronic118 in long-term use is reduced, so that the problem that a segregation modifier is lost in the preparation and use processes of the ultrafiltration membrane is solved, and the hydrophilicity, the pollution resistance and the long-term use stability of the surface of the ultrafiltration membrane are improved.
The invention is suitable for preparing the durable high-performance ultrafiltration membrane.
Drawings
FIG. 1 is a graph showing five changes in the flux of the control group in the five cycles of filtration of 0.1g/L BSA by an ultrafiltration membrane without addition of beta-cyclodextrin;
FIG. 2 is a graph showing five changes in the flux of bovine serum albumin of the durable high performance ultrafiltration membrane prepared in example 1;
FIG. 3 is a graph showing five changes in the flux of bovine serum albumin of the durable high performance ultrafiltration membrane prepared in example 2;
FIG. 4 is a graph showing the five-cycle flux changes of bovine serum albumin for the durable high-performance ultrafiltration membrane prepared in example 3;
FIG. 5 is a graph showing five changes in the flux of bovine serum albumin of the durable high performance ultrafiltration membrane prepared in example 4;
FIG. 6 is a graph showing five changes in the flux of bovine serum albumin of the durable high performance ultrafiltration membrane prepared in example 5.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the embodiment is a method for preparing a durable high-performance ultrafiltration membrane based on a supermolecular assembly reinforced blending method, which comprises the following steps:
1. mixing beta-cyclodextrin, pluronic F118, PES and DMAC, mechanically stirring for 20-26 h at 65-75 ℃, and defoaming to obtain a casting solution;
2. the casting solution is uniformly cast on a smooth polished fine glass plate after being cooled, and the membrane is taken down and cleaned after being solidified, thus completing the method for preparing the durable high-performance ultrafiltration membrane based on the supermolecular assembly reinforced blending method;
wherein the casting thickness of the casting solution in the second step is 240-260 μm.
The ultrafiltration membrane prepared in the embodiment is stored in deionized water for at least 12 hours and then is used.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the dosage of the beta-cyclodextrin in the first step: 1wt%, 3wt%, 4wt%, 5wt% or 7wt% of the total amount of PES. Other steps and parameters are the same as those in the first embodiment.
The third concrete implementation mode: this embodiment differs from the first or second embodiment in that the amount of Pluronic F118 used in step one: accounting for 30wt percent to 40wt percent of the total weight of PES. Other steps and parameters are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is that the dosage of PES in step one: accounting for 12wt percent to 18wt percent of the total weight of the casting solution. Other steps and parameters are the same as those in one of the first to third embodiments.
The fifth concrete implementation mode: this embodiment differs from one of the first to fourth embodiments in that in the first step the PES is Pasteur 3000P, germany, having a relative molecular weight of 2X 10 4 ～5×10 5 . Other steps and parameters are the same as in one of the first to fourth embodiments.
The sixth specific implementation mode: this embodiment differs from one of the first to fifth embodiments in that the Pluronic118 in step one has a relative molecular weight of 14600. Other steps and parameters are the same as in one of the first to fifth embodiments.
The seventh embodiment: the present embodiment is different from the first to sixth embodiments in that the defoaming in the first step: standing in 50 deg.C water bath for 4 hr. Other steps and parameters are the same as those in one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment is different from the first to seventh embodiments in that the casting solution in the second step is cooled to 23 to 27 ℃. Other steps and parameters are the same as those in one of the first to seventh embodiments.
The specific implementation method nine: this embodiment differs from the first to eighth embodiments in that the solidification in the second step: placing the mixture in deionized water solution at the temperature of 22-27 ℃ for coagulation for 8-12 min. Other steps and parameters are the same as those in one to eight of the embodiments.
The detailed implementation mode is ten: the difference between this embodiment and the first to ninth embodiments is that the cleaning in the second step: and cleaning for 2-3 times by using deionized water. Other steps and parameters are the same as those in one of the first to ninth embodiments.
The concrete implementation mode eleven: this embodiment differs from the first to tenth embodiments in that the ultrafiltration membrane produced is stored in deionized water for at least 12 hours and then used. Other steps and parameters are the same as in one of the first to tenth embodiments.
The beneficial effects of the present invention are demonstrated by the following examples:
control group:
ultrafiltration membranes without added beta-cyclodextrin: firstly, 1.28g of Pluronic F118, 3.2g of PES and 15.52g of DMAC are mixed, mechanically stirred for about 24 hours at 70 ℃ to make the mixture uniform, and then kept stand in a water bath at 50 ℃ for 4 hours to complete defoaming; then cooling the obtained casting solution to 25 ℃, and uniformly casting the casting solution on a smooth polished fine glass plate with the thickness of 250 mu m by using a film scraping knife; and finally, solidifying the glass plate with the liquid film in a deionized water solution at 25 ℃ for 10min, taking the obtained ultrafiltration membrane out of the glass plate, and thoroughly cleaning the ultrafiltration membrane by using deionized water. The prepared film was stored in deionized water for at least 12 hours before use.
Example 1:
1. mixing 0.032g (namely 1 wt%) of beta-cyclodextrin, 1.28g of Pluronic F118, 3.2g of PES and 15.52g of DMAC, mechanically stirring for 24 hours at 70 ℃, and defoaming to obtain a casting solution;
2. the casting solution is uniformly cast on a smooth polished fine glass plate after being cooled, and the membrane is taken down and cleaned after being solidified, thus completing the method for preparing the durable high-performance ultrafiltration membrane based on the supermolecular assembly reinforced blending method;
wherein the casting thickness of the casting solution in the second step is 250 μm.
In the first step of this example, PES was Pasf 3000P, with a relative molecular weight of 4X 10 5 。
The Pluronic118 described in step one of this example had a relative molecular weight of 14600.
In the first step of this embodiment, the defoaming: standing in 50 deg.C water bath for 4 hr.
In the second step of this example, the casting solution was cooled to 25 ℃.
In the second step of this embodiment, the solidification: placing in deionized water solution at 25 deg.C for solidifying for 10min.
In the second step of this embodiment: and washing with deionized water for 3 times.
The ultrafiltration membrane prepared in this example was stored in deionized water for at least 12 hours before use.
Example 2:
the amount of beta-cyclodextrin used in this example was 0.096g, (i.e., 3 wt%); the remaining steps and parameters were the same as in example 1.
Example 3:
the amount of beta-cyclodextrin used in this example was 0.128g, (i.e., 4 wt%); the remaining steps and parameters were the same as in example 1.
Example 4:
the amount of beta-cyclodextrin used in this example was 0.160g, (i.e., 5 wt%); the remaining steps and parameters were the same as in example 1.
Example 5:
the amount of beta-cyclodextrin used in this example was 0.224g, (i.e., 7 wt%); the remaining steps and parameters were the same as in example 1.
The ultrafiltration membranes prepared in the control group and examples 1 to 5 were tested for five changes in circulating flux of 0.1g/L BSA. The content of each circulation is as follows: pure water (30 min) -bovine serum albumin solution (60 min) -washing (20 min, not shown) -pure water (30 min). The average tangential water flow rate was 180r/min.
The control group contained the ultrafiltration membrane without beta-cyclodextrin, and the flux of Bovine Serum Albumin (BSA) at 0.1g/L changed five times, as shown in FIG. 1, the basic flux of the ultrafiltration membrane without beta-cyclodextrin was 301.46Lm -2 h -1 bar -1 The flux of filtered pure water after cycle 1 wash was 81.57% of the base flux. The 5 th cycle bovine serum albumin filtration flux was 25.06% of the basal flux, and the pure water filtration flux was 52.59% of the basal flux. The bovine serum albumin retention rate is more than 99.9%.
Example 1 five cycles of flux changes in bovine serum albumin for the permanent high performance ultrafiltration membrane prepared, as shown in fig. 2, the fundamental flux of the permanent high performance ultrafiltration membrane was 366.03Lm -2 h -1 bar -1 The flux of filtered pure water after cycle 1 wash was 86.19% of the base flux. The 5 th cycle bovine serum albumin filtration flux was 28.62% of the base flux, and the pure water filtration flux was 55.99% of the base flux. The bovine serum albumin retention rate is more than 99.9%.
Five changes in the flux of bovine serum albumin of the permanent high-performance ultrafiltration membrane prepared in example 2, as shown in fig. 3, the basic flux of the permanent high-performance ultrafiltration membrane is 360.44Lm -2 h -1 bar -1 The flux of filtered pure water after cycle 1 wash was 84.91% of the basal flux. The 5 th cycle bovine serum albumin filtration flux was 36.00% of the basal flux, and the pure water filtration flux was 58.48% of the basal flux. The bovine serum albumin retention rate is more than 99.9%.
The bovine serum albumin of the durable high-performance ultrafiltration membrane prepared in example 3 has five changes in the circulating flux, and as shown in fig. 4, the basic flux of the durable high-performance ultrafiltration membrane is 338.68Lm -2 h -1 bar -1 And the flux of filtered pure water after the 1 st cycle of cleaning is 96.85% of the basic flux. The 5 th cycle bovine serum albumin filtration flux was 54.53% of the base flux, and the pure water filtration flux was 97.80% of the base flux. The bovine serum albumin retention rate is more than 99.9%.
Example 4 five cycles of flux changes of bovine serum albumin for the resulting durable high performance ultrafiltration membrane, as shown in fig. 5, the base flux of the resulting durable high performance ultrafiltration membrane was 342.74Lm -2 h -1 bar -1 The flux of filtered pure water after cycle 1 wash was 98.67% of the base flux. The 5 th cycle bovine serum albumin filtration flux was 72.24% of the basal flux, and the pure water filtration flux was 92.23% of the basal flux. The bovine serum albumin retention rate is more than 99.9%.
Five changes in the flux of bovine serum albumin of the permanent high-performance ultrafiltration membrane prepared in example 5 are shown in FIG. 6, and the basic flux of the permanent high-performance ultrafiltration membrane is 185.85Lm -2 h -1 bar -1 And the flux of filtered pure water after cycle 1 washing was 87.00% of the basic flux. Cycle 5 bovine serum albumin filtration flux based54.78% of the amount, and the flux of pure filtered water was 70.19% of the base flux. The bovine serum albumin retention rate is more than 99.9%.
In conclusion, the method for preparing the durable high-performance ultrafiltration membrane based on the supermolecular assembly reinforced blending method can be used for preparing the durable high-performance ultrafiltration membrane through self-assembly of beta-cyclodextrin, PES and Pluronic F118, the membrane performance can be regulated and controlled through the addition of the beta-cyclodextrin, and when the addition of the beta-cyclodextrin accounts for 4-5 wt% of PES as a membrane main polymer, the comprehensive performance of the membrane is optimal.
Although the present invention has been described in connection with the accompanying drawings, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than restrictive, and many modifications may be made by those skilled in the art without departing from the spirit of the present invention as disclosed in the appended claims.
Claims (10)
1. A method for preparing a durable high-performance ultrafiltration membrane based on a supermolecule assembly strengthening blending method is characterized by comprising the following steps:
1. mixing beta-cyclodextrin, pluronic F118, PES and DMAC, mechanically stirring for 20-26 h at 65-75 ℃, and defoaming to obtain a casting solution;
2. the casting solution is uniformly cast on a smooth polished fine glass plate after being cooled, and the membrane is taken down and cleaned after being solidified, thus completing the method for preparing the durable high-performance ultrafiltration membrane based on the supermolecular assembly reinforced blending method;
wherein the casting thickness of the casting solution in the second step is 240-260 μm.
2. The method for preparing the durable high-performance ultrafiltration membrane based on the supramolecular assembly reinforced blending method according to claim 1, wherein the dosage of the beta-cyclodextrin in the step one is as follows: 1wt%, 3wt%, 4wt%, 5wt% or 7wt% of the total amount of PES.
3. The method for preparing the durable high-performance ultrafiltration membrane based on the supramolecular assembly reinforced blending method as claimed in claim 1, wherein the dosage of Pluronic F118 in the step one is as follows: accounting for 30wt percent to 40wt percent of the total weight of PES.
4. The method for preparing the durable high-performance ultrafiltration membrane based on the supramolecular assembly reinforced blending method as claimed in claim 1, wherein the dosage of PES in step one is as follows: accounting for 12wt percent to 18wt percent of the total weight of the casting solution.
5. The method for preparing the durable high-performance ultrafiltration membrane based on the supramolecular assembly reinforced blending method according to claim 1, wherein the PES in the step one is German Pasteur 3000P, and the relative molecular weight of the PES is 2 x 10 4 ～5×10 5 。
6. The method for preparing the durable high-performance ultrafiltration membrane based on the supramolecular assembly reinforced blending method as claimed in claim 1, wherein the relative molecular weight of Pluronic118 in the first step is 14600.
7. The method for preparing the durable high-performance ultrafiltration membrane based on the supramolecular assembly reinforced blending method according to claim 1, wherein the defoaming in the step one is as follows: standing in 50 deg.C water bath for 4 hr.
8. The method for preparing the durable high-performance ultrafiltration membrane based on the supramolecular assembly reinforced blending method according to claim 1, wherein the membrane casting solution is cooled to 23-27 ℃ in the second step.
9. The method for preparing the durable high-performance ultrafiltration membrane based on the supramolecular assembly reinforced blending method according to claim 1, wherein the coagulation in the step two is as follows: placing the mixture in deionized water solution at the temperature of 22-27 ℃ for coagulation for 8-12 min.
10. The method for preparing the durable high-performance ultrafiltration membrane based on the supramolecular assembly reinforced blending method according to claim 1, wherein the cleaning in the step two is as follows: and washing with deionized water for 2-3 times.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5006256A (en) * | 1988-01-14 | 1991-04-09 | The Standard Oil Company | Affinity membranes having pendant hydroxy groups and processes for the preparation and use thereof |
| CN101259387A (en) * | 2007-12-19 | 2008-09-10 | 天津大学 | Controllable-flux protein-pollution-resistance poly (ether-sulfone) ultrafiltration membrane and preparation |
| CN104804198A (en) * | 2015-04-23 | 2015-07-29 | 吉林大学 | Self-supporting two-dimensional single-layered supramolecular polymer and application of two-dimensional single-layered supramolecular polymer in nano separation membrane |
| CN108654385A (en) * | 2018-04-26 | 2018-10-16 | 天津大学 | A kind of preparation method having both highly selective high osmosis ultrafiltration membrane |
| CN112044291A (en) * | 2020-09-23 | 2020-12-08 | 天津工业大学 | Compact separation membrane |
| CN114130212A (en) * | 2021-11-30 | 2022-03-04 | 天津工业大学 | Method for preparing separation membrane by using small molecule monomer |
| WO2022183751A1 (en) * | 2021-03-05 | 2022-09-09 | 中国石油化工股份有限公司 | Double-continuous high-pass polymer ultrafiltration membrane, preparation method therefor, and application thereof |
-
2022
- 2022-12-08 CN CN202211582835.3A patent/CN115738743B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5006256A (en) * | 1988-01-14 | 1991-04-09 | The Standard Oil Company | Affinity membranes having pendant hydroxy groups and processes for the preparation and use thereof |
| CN101259387A (en) * | 2007-12-19 | 2008-09-10 | 天津大学 | Controllable-flux protein-pollution-resistance poly (ether-sulfone) ultrafiltration membrane and preparation |
| CN104804198A (en) * | 2015-04-23 | 2015-07-29 | 吉林大学 | Self-supporting two-dimensional single-layered supramolecular polymer and application of two-dimensional single-layered supramolecular polymer in nano separation membrane |
| CN108654385A (en) * | 2018-04-26 | 2018-10-16 | 天津大学 | A kind of preparation method having both highly selective high osmosis ultrafiltration membrane |
| CN112044291A (en) * | 2020-09-23 | 2020-12-08 | 天津工业大学 | Compact separation membrane |
| WO2022183751A1 (en) * | 2021-03-05 | 2022-09-09 | 中国石油化工股份有限公司 | Double-continuous high-pass polymer ultrafiltration membrane, preparation method therefor, and application thereof |
| CN114130212A (en) * | 2021-11-30 | 2022-03-04 | 天津工业大学 | Method for preparing separation membrane by using small molecule monomer |
Non-Patent Citations (2)
| Title |
|---|
| LG LIN: "A Supramolecular Strategy for Self-Mobile Adsorption Sites in Affinity Membrane", MACROMOLECULAR RAPID COMMUNICATIONS, vol. 35, no. 18, pages 1587 - 1591 * |
| 彭冬冬;贺明睿;杨昊;张蓓;高博鑫;范琳;丁鹤;南延虎;潘福生;苏延磊;吴洪;姜忠义;: "仿生与生物启发膜的研究进展", 中国工程科学, no. 12, pages 104 - 114 * |
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