CN111359457B - A kind of sulfonated polyaryl ether sulfone nanofiltration membrane and preparation method thereof - Google Patents
A kind of sulfonated polyaryl ether sulfone nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN111359457B CN111359457B CN202010255833.8A CN202010255833A CN111359457B CN 111359457 B CN111359457 B CN 111359457B CN 202010255833 A CN202010255833 A CN 202010255833A CN 111359457 B CN111359457 B CN 111359457B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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Abstract
本发明提供了一种磺化聚芳醚砜纳滤膜的制备方法，属于膜分离材料制备领域。The invention provides a preparation method of a sulfonated polyaryl ether sulfone nanofiltration membrane, which belongs to the field of membrane separation material preparation.
Description
Technical Field
The invention belongs to the field of preparation of membrane separation materials, and particularly relates to a sulfonated polyarylethersulfone nanofiltration membrane and a preparation method thereof.
Background
The polyarylethersulfone material is a special engineering plastic which integrates the characteristics of easy molding and processing and high impact strength, has excellent dimensional stability, thermal stability, mechanical stability and good biocompatibility, and is widely applied to the fields of medicine, transportation, electronic and electric appliances and the like due to the advantages of excellent performance and low price. However, the hydrophobic nature of polyethersulfones limits their use and thus modification is required to increase hydrophilicity. The common modification method at present introduces sulfonic acid groups in a sulfonation mode, and the modified sulfonated polyether sulfone material has good hydrophilicity, acid and alkali resistance and chlorine resistance, and can be applied to the fields of fuel cell membranes, reverse osmosis membranes, ultrafiltration membranes and the like.
The sulfonated polyarylethersulfone membrane material has good mechanical property, chemical stability and thermal stability, low methanol permeability and low price, and the waste sulfonated polyarylethersulfone membrane is easy to degrade and does not pollute the environment, so the sulfonated polyarylethersulfone membrane material is expected to become a polyelectrolyte membrane material of a new generation. The invention provides a brand-new sulfonated polyarylethersulfone polymer, which has a simple preparation method and has great potential application value in the fields of fuel cell membranes, reverse osmosis membranes, ultrafiltration membranes and the like.
The nanofiltration membrane is a new field of membrane separation technology in recent years, has the characteristics of low operation pressure, energy conservation and the like, and is widely applied at present.
Disclosure of Invention
The invention provides a preparation method of a nanofiltration membrane, which is characterized by comprising the following steps:
step 1: adding sulfonated polyarylethersulfone into an organic solvent, heating to 50-100 ℃ under the condition of stirring, and dissolving until the sulfonated polyarylethersulfone is clear;
step 2: defoaming the solution obtained in the step 1;
and step 3: cooling the casting solution prepared in the step 2 to room temperature, pouring the casting solution on a glass plate or non-woven fabric, and scraping a nascent state membrane;
and 4, step 4: after the solvent in the nascent-state membrane is volatilized for 1-600 seconds, immersing the nascent-state membrane in deionized water at the temperature of 0-70 ℃ for solidification to form a membrane;
and 5: washing the membrane in the step 4 with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane,
wherein the sulfonated polyarylethersulfone has a structure as shown in formula (IA),
in some embodiments of the present invention, the organic solvent is selected from the group consisting of N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
In some embodiments of the present invention, the heating temperature in step 1 is 50-70 ℃.
In some embodiments of the present invention, the heating and stirring time in step 1 is 2 to 48 hours.
In some embodiments of the present invention, the heating and stirring time in step 1 is 12 to 36 hours.
In some schemes of the invention, the defoaming temperature is 30-60 ℃.
In some embodiments of the present invention, the defoaming temperature is 40 to 50 ℃.
In some schemes of the invention, the defoaming temperature is 35-45 ℃.
In some embodiments of the present invention, the defoaming time is 1 to 24 hours.
In some embodiments of the present invention, the defoaming time is 2 to 12 hours.
In some embodiments of the present invention, the defoaming time is 4 to 8 hours.
In some embodiments of the present invention, the volatilization time of the solvent in the nascent membrane is 60 to 200 seconds.
In some embodiments of the present invention, the volatilization time of the solvent in the nascent membrane is 60 to 150 seconds.
In some embodiments of the present invention, the volatilization time of the solvent in the nascent-state membrane is 60 to 120 seconds.
In some embodiments of the present invention, the volatilization time of the solvent in the nascent membrane is 90 to 120 seconds.
In some schemes of the invention, the nascent state membrane is immersed in deionized water at 30-60 ℃ for solidification to form the membrane.
In some schemes of the invention, the nascent state membrane is immersed in deionized water at 35-55 ℃ for solidification to form the membrane.
In some schemes of the invention, the nascent state membrane is immersed in deionized water at 40-50 ℃ for solidification to form the membrane.
In some schemes of the invention, the concentration of the sulfonated polyarylethersulfone in the membrane casting solution is 20-40 wt%.
In some schemes of the invention, the concentration of the sulfonated polyarylethersulfone in the membrane casting solution is 25-35 wt%.
In some schemes of the invention, the concentration of the sulfonated polyarylethersulfone in the membrane casting solution is 28-32 wt%.
In some embodiments of the present invention, the thickness of the nascent membrane is 50 to 300 μm.
In some embodiments of the present invention, the thickness of the nascent membrane is 100 to 300 μm.
The invention has the beneficial effects that:
the invention provides a chemical polyarylethersulfone nanofiltration membrane with a brand new structure, which is simple in preparation method, has excellent water flux and separation performance, and has great potential industrial application value.
Detailed Description
The following detailed description of specific embodiments of the present invention is provided to illustrate and explain the present invention and to be understood not to limit the present invention.
Example 1: synthesis of sulfonated Polyarylethersulfone (IA)
Step 1: synthesis of 3,3' - (sulfonylbis (6-fluoro-3, 1-phenylene)) bisquinoline (I-c)
4,4' -sulfonylbis (2-bromo-1-fluorobenzene) (8.24g, 20mmol) was dissolved in 100mL of tetrahydrofuran, 0.2g of tetrakis (triphenylphosphine) palladium was added, quinoline-3-boronic acid (7.26g, 42mmol) was added, and the mixture was heated under reflux for 12 hours under nitrogen protection. After the reaction was completed, 100mL of water was added thereto, and the mixture was stirred for 1 hour and filtered to obtain a crude product of 3,3'- (sulfonylbis (6-fluoro-3, 1-phenylene)) biquinoline, which was recrystallized from toluene to obtain 8.63g of a crude product of 3,3' - (sulfonylbis (6-fluoro-3, 1-phenylene)) biquinoline in a yield of 85%.
MS m/z：509.2[M+H]+
Step 2: synthesis of polyarylethersulfone (I-e)
3,3'- (sulfonylbis (6-fluoro-3, 1-phenylene)) bisquinoline (5.08g, 10mmol), 4' - (1, 3-dioxolan-2, 2-diyl) diphenol (2.89g, 11.5mmol), anhydrous potassium carbonate (1.59g, 11.5mmol), N-methylpyrrolidone (40mL) and toluene (10mL) were charged into a reaction flask, and reacted under reflux for 10 hours while the water separator removed the water in the system. Evaporating toluene in the system, continuing to react for 7 hours at 160 ℃, after the reaction is finished, slowly dropwise adding absolute ethyl alcohol (200mL) into the reaction liquid within 3 hours, stirring to separate out a large amount of white solid, continuing to stir for 1 hour, and filtering to obtain polyarylether sulfone (I-e) (6.47g, yield 83%).
And step 3: preparation of sulfonated polyarylethersulfones (Ia)
Dissolving polyarylethersulfone (I-e) (3.6g, 5mmol) in concentrated sulfuric acid (100mL), heating to 45 ℃, stirring for 5 hours, after the reaction is finished, slowly dripping the reaction liquid into 2L of ice water under the condition of vigorous stirring, continuing stirring for 1 hour after dripping is finished, and filtering to obtain sulfonated polyarylethersulfone (IA).
Example 2: preparation of sulfonated polyarylethersulfone nanofiltration membrane 1
Adding sulfonated polyarylethersulfone (IA) (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the condition of stirring, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing for 12 hours at 60 ℃ for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 60 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at the temperature of 40 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 1.
Example 3: preparation of sulfonated polyarylethersulfone nanofiltration membrane 2
Adding sulfonated polyarylethersulfone (IA) (2.8g) into N-methylpyrrolidone (7.2g), heating to 60 ℃ under the condition of stirring, completely dissolving the sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing at 60 ℃ for 12 hours for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 60 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at the temperature of 40 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 2.
Example 4: preparation of sulfonated polyarylethersulfone nanofiltration membrane 3
Adding sulfonated polyarylethersulfone (IA) (3.2g) into N-methylpyrrolidone (6.8g), heating to 60 ℃ under the condition of stirring, completely dissolving the sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing at 60 ℃ for 12 hours for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 60 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at the temperature of 40 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 3.
Example 5: preparation of sulfonated poly (aryl ether sulfone) nanofiltration membrane 4
Adding sulfonated polyarylethersulfone (IA) (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the condition of stirring, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing for 12 hours at 60 ℃ for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 60 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at the temperature of 30 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 4.
Example 6: preparation of sulfonated polyarylethersulfone nanofiltration membrane 5
Adding sulfonated polyarylethersulfone (IA) (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the condition of stirring, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing for 12 hours at 60 ℃ for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 60 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at 50 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 5.
Example 7: preparation of sulfonated polyarylethersulfone nanofiltration membrane 6
Adding sulfonated polyarylethersulfone (IA) (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the condition of stirring, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing for 12 hours at 60 ℃ for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 40 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at the temperature of 50 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 6.
Example 8: preparation of sulfonated poly (aryl ether sulfone) nanofiltration membrane 7
Adding sulfonated polyarylethersulfone (IA) (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the condition of stirring, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing for 12 hours at 60 ℃ for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 90 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at 50 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane 7.
Example 9: preparation of control nanofiltration membranes
Adding Nafion (3g) into N-methylpyrrolidone (7g), heating to 60 ℃ under the stirring condition, dissolving all sulfonated polyarylethersulfone (IA), continuously stirring for 12 hours to obtain a uniform membrane casting solution, and standing at 60 ℃ for 12 hours for defoaming. Pouring the defoamed casting solution on a clean glass plate, and scraping the casting solution into a uniform nascent state membrane with the diameter of 100 mu m by using a scraper. After the nascent state membrane is volatilized for 90 seconds, the nascent state membrane is taken down on a glass plate and slowly put into deionized water at 50 ℃ to be solidified into a membrane. And washing the membrane with deionized water for 3 times to obtain a control nanofiltration membrane.
Experimental example 1: water absorption test
Homogeneous sulfonated poly (aryl ether sulfone) (I-B) and Nafion membrane are soaked in deionized water for 24h under the test conditions of 25 ℃ and 80 ℃, and then the mass Mw of the soaked homogeneous membrane is weighed by an analytical balance. And (3) putting the soaked sample into a vacuum drying oven, drying for 24 hours at 75 ℃, weighing the mass Md of the dry film after the sample is completely dried, and calculating the water absorption rate according to the formula of (Mw-Md)/Md x 100%. The results of the experiment are shown in table 1.
Experimental example 2: measurement of ion exchange Capacity
Weighing fully dried sulfonated polyarylethersulfone (I-B) and a Nafion blank membrane (weight is recorded as M), dissolving the sulfonated polyarylethersulfone (I-B) and the Nafion blank membrane by using N-methylpyrrolidone as a solvent and 10 mLN-methylpyrrolidone, adding 10mL of deionized water after fully dissolving, using methyl red as an indicator, titrating by using a calibrated NaOH solution (concentration is recorded as C1) (the volume consumed by NaOH is recorded as V1), testing for 3 times, and calculating the ion exchange capacity by using a formula (2), wherein the formula is IEC (V1) and C1/M. The results of the experiment are shown in table 1.
TABLE 1
Experimental example 3: nanofiltration test experiment
The experiment adopts a cross-flow filtration method: under the conditions of 25 ℃ of temperature, 0.6MPa of pressure and 18.1cm of effective area 2, 2g/L magnesium sulfate solution is adopted as test feed liquid, the membrane is pre-pressed to ensure that the permeability of the membrane is stable, then flux and interception are measured once every 5 minutes, and the average value is taken as the final test result after 3 times of tests. The membrane flux J is calculated as J ═ V/(A ×) and V is the volume of the permeation flux, A is the area of the effective membrane and t is the time; the retention rate R is calculated by the formula of R ═ 1-Cp/Cf)*100％，CpAs the concentration of the feed solution, CfIs the permeate concentration.
The test results of the sulfonated polyarylethersulfone nanofiltration membranes 1-7 and the control nanofiltration membrane are shown in table 2.
TABLE 2
| Test sample | Flow rate (L/(m)2*h)) | Retention (%) |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 1 | 51.3 | 79.8 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 2 | 51.1 | 78.7 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 3 | 49.8 | 81.2 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 4 | 54.6 | 73.8 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 5 | 50.5 | 80.3 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 6 | 51.0 | 79.1 |
| Sulfonated poly (aryl ether sulfone) nanofiltration membrane 7 | 50.6 | 78.8 |
| Control nanofiltration membranes | 43.7 | 76.5 |
The results show that the sulfonated polyarylethersulfone nanofiltration membrane has higher water flux, higher retention rate and excellent separation effect.
Claims (8)
1. The preparation method of the nanofiltration membrane is characterized by comprising the following steps:
step 1: adding sulfonated polyarylethersulfone into an organic solvent, heating to 50-100 ℃ under the condition of stirring, and dissolving until the sulfonated polyarylethersulfone is clear;
step 2: defoaming the solution obtained in the step 1;
and step 3: cooling the casting solution prepared in the step 2 to room temperature, pouring the casting solution on a glass plate or non-woven fabric, and scraping a nascent state membrane;
and 4, step 4: after the solvent in the nascent-state membrane is volatilized for 1-600 seconds, immersing the nascent-state membrane in deionized water at the temperature of 0-70 ℃ for solidification to form a membrane;
and 5: washing the membrane in the step 4 with deionized water for 3 times to obtain the sulfonated polyarylethersulfone nanofiltration membrane,
wherein the sulfonated polyarylethersulfone has a structure as shown in formula (IA),
2. nanofiltration membrane preparation method according to claim 1, wherein the organic solvent is selected from the group consisting of N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
3. The nanofiltration membrane preparation method according to claim 1, wherein the deaeration temperature is 30-60 ℃.
4. The nanofiltration membrane preparation method according to claim 1, wherein the defoaming time is 1-24 hours.
5. The nanofiltration membrane preparation method according to claim 1, wherein the volatilization time of the solvent in the nascent membrane is 60-200 seconds.
6. The nanofiltration membrane preparation method according to claim 1, wherein the nascent membrane is immersed in deionized water at 30-60 ℃ to be solidified into a membrane.
7. The nanofiltration membrane preparation method according to claim 1, wherein the concentration of the sulfonated polyarylethersulfone in the membrane casting solution is 20-40 wt%.
8. The nanofiltration membrane preparation method according to claim 1, wherein the thickness of the nascent membrane is 50-300 μm.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583831A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Benzimidazole with sulfonate as side group and benzoxaazole copolymer and its preparation |
| CN101238602A (en) * | 2005-07-15 | 2008-08-06 | 捷时雅株式会社 | Electrolyte for Solid Polymer Fuel Cell |
| US20090221787A1 (en) * | 2005-07-09 | 2009-09-03 | Thomas Haring | Production Of Monomer, Oligomer And Polymer Phosphonic Acid Esters And Phosphonic And Sulphonic Acids By A Nucleophile Aromatic Substitution |
| CN101724165A (en) * | 2009-11-20 | 2010-06-09 | 清华大学 | Epoxy crosslinking sulfonated polyaryletherketone proton exchange membrane material and preparation method thereof |
| CN102558557A (en) * | 2010-12-02 | 2012-07-11 | 现代自动车株式会社 | Poly (arylene ether) copolymer having cation exchange group, method for producing the same, and use thereof |
| CN103506016A (en) * | 2012-06-29 | 2014-01-15 | 南京理工大学 | Novel sulfonated polyarylether sulfone water treatment ultrafiltration membrane and preparation method thereof |
| CN110527093A (en) * | 2019-08-15 | 2019-12-03 | 温州大学 | A kind of the sulfonation Cardo polyether sulfone polymer and synthetic method, reverse osmosis composite membrane of amino-contained |
-
2020
- 2020-04-02 CN CN202010255833.8A patent/CN111359457B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583831A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Benzimidazole with sulfonate as side group and benzoxaazole copolymer and its preparation |
| US20090221787A1 (en) * | 2005-07-09 | 2009-09-03 | Thomas Haring | Production Of Monomer, Oligomer And Polymer Phosphonic Acid Esters And Phosphonic And Sulphonic Acids By A Nucleophile Aromatic Substitution |
| CN101238602A (en) * | 2005-07-15 | 2008-08-06 | 捷时雅株式会社 | Electrolyte for Solid Polymer Fuel Cell |
| CN101724165A (en) * | 2009-11-20 | 2010-06-09 | 清华大学 | Epoxy crosslinking sulfonated polyaryletherketone proton exchange membrane material and preparation method thereof |
| CN102558557A (en) * | 2010-12-02 | 2012-07-11 | 现代自动车株式会社 | Poly (arylene ether) copolymer having cation exchange group, method for producing the same, and use thereof |
| CN103506016A (en) * | 2012-06-29 | 2014-01-15 | 南京理工大学 | Novel sulfonated polyarylether sulfone water treatment ultrafiltration membrane and preparation method thereof |
| CN110527093A (en) * | 2019-08-15 | 2019-12-03 | 温州大学 | A kind of the sulfonation Cardo polyether sulfone polymer and synthetic method, reverse osmosis composite membrane of amino-contained |
Non-Patent Citations (2)
| Title |
|---|
| 一类侧链型磺化聚芳醚砜质子交换膜的合成及表征;沈斌等;《高分子学报》;20161031(第10期);第1409-1417页 * |
| 磺化含侧苯基杂萘联苯聚芳醚砜膜材料的制备与性能;柳周洋等;《膜科学与技术》;20191031;第39卷(第5期);第87-93页 * |
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