CN105771677B - Sodium alginate/covalent organic framework composite membrane and preparation and application - Google Patents
Sodium alginate/covalent organic framework composite membrane and preparation and application Download PDFInfo
- Publication number
- CN105771677B CN105771677B CN201610103809.6A CN201610103809A CN105771677B CN 105771677 B CN105771677 B CN 105771677B CN 201610103809 A CN201610103809 A CN 201610103809A CN 105771677 B CN105771677 B CN 105771677B
- Authority
- CN
- China
- Prior art keywords
- organic framework
- covalent organic
- sodium alginate
- composite membrane
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
It the invention discloses a kind of sodium alginate/covalent organic framework composite membrane, is made of sodium alginate and covalent organic framework 100:5~30 in mass ratio；Wherein, covalent organic framework is formed by terephthalaldehyde and the melamine polycondensation of 1~1.5:1 in mass ratio.Its preparation step is: using terephthalaldehyde and melamine as monomer, polycondensation reaction is carried out in dimethyl sulfoxide solvent, product successively after methanol, tetrahydrofuran, methanol extraction, obtains covalent organic framework；Covalent organic framework is distributed in deionized water, is mixed to form casting solution with sodium alginate, it is crosslinked, be dried to obtain the composite membrane after being spun on polyacrylonitrile ultrafiltration film.The present invention has many advantages, such as that preparation process is easy, controllability is strong, raw material is easy to get, method is general.Composite membrane obtained is used for pervaporation ethanol-water solution system, has high permeating flux, highly selective to hydrone, while the composite membrane has good operational stability at high temperature.
Description
Technical field
The present invention relates to a kind of sodium alginate/covalent organic framework composite membrane and preparations and application, and it is organic to belong to macromolecule-
Composite membrane technology field.
Background technique
The energy and environment are two significant challenges that the 21 century whole world faces, and AND ENERGY RESOURCES CONSUMPTION IN CHINA increasingly increases, disappears every year
Energy consumption adds up to about 400,000,000 tons of standard coals.Therefore, country has put into effect multinomial policies and regulations, carries forward vigorously renewable energy, especially
It is the development of biomass energy, and carries out the application of alcohol fuel gasoline in China.Fuel is produced by raw material of biomass
In the process of ethyl alcohol, the water smoking is directed to the azeotropic mixture of second alcohol and water, energy consumption height (account for about total energy consumption 20%), separating difficulty
Greatly.Common dewatering is special extract rectification method and absorption method, and special extract rectification method process is complicated, and energy consumption is higher；Though absorption method work
Skill is relatively easy, but belongs to intermittently operated.Compared with the above two, Pervaporation can be produced greatly in simplification of flowsheet, reduction
Energy consumption has very big development potentiality.
Process of pervaporation follows dissolution-diffusion mechanism, using the physical difference of second alcohol and water, can strengthen respectively and dissolve
Journey and diffusion process.However permeability and selectivity that membrane material is shifting --- tradeoff effect are always high-performance
The bottleneck of membrane material preparation.A large number of studies show that inorganic filler can improve the network structure of polymer matrix, macromolecule is adjusted
Chain spacing and chain rigidity, the close and distant water balance of adjusting film introduce additional transmission channels and screening function etc., to overcome Trade-
Off effect.However interface interaction is poor between macromolecule and inorganic particle, defect is easily formed, to influence the stability of film.
To improve permeability of the membrane, selectivity and stability simultaneously, this researching and designing prepares the more function of covalent organic framework
Energy material, and fill it into and prepare composite membrane in sodium alginate, it is intended to utilize the hydrophily of covalent organic framework to promote water
Molecule Preferential adsorption realizes that the selectivity of hydrone is spread using the specific pore size of covalent organic framework.Furthermore covalently have
Machine skeleton is the stabilizing material formed by strong covalent bond, and it is organic framework structured have between polymeric hydantoin mosanom it is better
Interface compatibility, thus the mechanical stability and thermal stability of membrane material can be improved.Up to the present, sodium alginate/covalently have
Machine skeleton composite membrane has no document report for pervaporation ethanol dehydration.
Summary of the invention
The present invention provides a kind of sodium alginate/covalent organic framework composite membrane and preparation method and application, the preparation method
Easy controllable, prepared composite membrane can be used for the dehydration of pervaporation ethanol-water system, separating property with higher and steady
Qualitative energy.
The present invention is to be realized by the following technical programs, a kind of sodium alginate/covalent organic framework composite membrane, should
Sodium alginate/covalent organic framework composite membrane is made of sodium alginate and covalent organic framework 100:5~30 in mass ratio；Its
In, covalent organic framework is formed by terephthalaldehyde and the melamine polycondensation of 1~1.5:1 in mass ratio, covalent organic framework
Partial size be 60~100nm, aperture be 0.4~0.6nm.
Above-mentioned sodium alginate/covalent organic framework composite membrane preparation method, steps are as follows:
Step 1: the preparation of covalent organic framework: melamine being dissolved in dimethyl sulfoxide solvent, mass body is formed
The solution that product concentration is 0.02~0.04g/mL, then presses and is added into solution to benzene two with 1~1.5:1 of melamine mass ratio
Formaldehyde；Argon gas-sealed is vigorously stirred and be passed through at 180 DEG C, is reacted 48~96h, is obtained tan precipitate object；By the sediment
Successively with being dried in vacuo for 24 hours after n,N-Dimethylformamide and tetrahydrofuran centrifuge washing, yellow powdery solid is obtained；It should
Yellow powdery solid is placed in Soxhlet extractor, 24 are respectively successively extracted using methanol, tetrahydrofuran, methanol at 80 DEG C~
48h, product extracted are dried in vacuo at 120 DEG C, finally obtain covalent organic framework；
Step 2: sodium alginate/covalent organic framework composite membrane film forming: covalent organic framework made from step 1 is molten
In deionized water, ultrasonic disperse 15min obtains dispersion liquid；Then dispersion liquid and a certain amount of sodium alginate are mixed to get
Solution A, wherein 0.05~0.3:1 of mass ratio of covalent organic framework and sodium alginate, quality of the sodium alginate in solution A
Score is 1.5%；Solution A stirs 4~6h at 30 DEG C with the revolving speed of 300r/min, and filtering is stood, after deaeration, obtains homogeneous
Casting solution；Casting solution is uniformly spun on polyacrylonitrile ultrafiltration film, drying at room temperature obtains composite membrane；Obtained composite membrane is soaked
Enter the CaCl of 0.5M2Be crosslinked in solution, taken out after 5~15min, with a large amount of deionized water flushing membrane calcium remained on surface from
Son；Composite membrane after crosslinking is dried at room temperature again, finally obtains sodium alginate/covalent organic framework composite membrane.
By above-mentioned sodium alginate/covalent organic framework composite membrane be used for pervaporation ethanol-water system dehydration, 76 DEG C,
Under conditions of material concentration is the ethanol water of mass fraction 90%, permeation flux is 1452~2397g/m2H, separation factor
It is 329~1293.
The present invention has the advantages that sodium alginate/covalent organic framework composite membrane preparation process is easy, controllability is strong, former
Material is easy to get, method is general.Composite membrane obtained is used for pervaporation ethanol-water solution system, logical with Thief zone to hydrone
It measures, is highly selective, while the composite membrane has good operational stability at high temperature.
Detailed description of the invention
Fig. 1 is the section electron microscope for the film 1 that embodiment 1 obtains.
Fig. 2 is the section electron microscope for the film 2 that embodiment 2 obtains.
Fig. 3 is the section electron microscope for the film 3 that embodiment 3 obtains.
Fig. 4 is the section electron microscope for the comparative film that comparative example obtains.
The permeation flux for the film that Fig. 5 is embodiment 1-3 and comparative example obtains and the comparison figure of separation factor.
Specific embodiment
Technical solution of the present invention is described in further detail with attached drawing combined with specific embodiments below, it is described specific
Embodiment is only explained the present invention, is not intended to limit the invention.
Embodiment 1 prepares sodium alginate/covalent organic framework composite membrane, and steps are as follows:
6g melamine is dissolved in 300mL dimethyl sulfoxide solvent, 6g terephthalaldehyde is then added.At 180 DEG C
Under be vigorously stirred and be passed through argon gas-sealed, after reacting 48h, obtain tan precipitate object.The sediment is successively used into N, N- diformazan
It is dried in vacuo for 24 hours after base formamide and tetrahydrofuran centrifuge washing, obtains yellow powdery solid.By the yellow powdery solid
Be placed in Soxhlet extractor, successively respectively extracted for 24 hours using methanol, tetrahydrofuran, methanol at 80 DEG C, product extracted in
It is dried in vacuo at 120 DEG C, obtains covalent organic framework；
It weighs covalent organic framework made from 0.019g step 1 to be dissolved in 25mL deionized water, ultrasonic disperse 15min is obtained
To dispersion liquid.Then 0.38g sodium alginate is added into dispersion liquid, obtained solution is stirred at 30 DEG C with the revolving speed of 300r/min
4h is mixed, filtering is stood, after deaeration, obtains homogeneous casting solution.Casting solution is uniformly spun on polyacrylonitrile ultrafiltration film, room temperature
It is dried to obtain composite membrane.Obtained composite membrane is immersed to the CaCl of 0.5M2It is crosslinked in solution, is taken out after 5min, and with greatly
Measure deionized water flushing membrane calcium ion remained on surface.Composite membrane after crosslinking is dried at room temperature again, finally obtains seaweed
Sour sodium/covalent organic framework composite membrane (film 1), the section electron microscope of film 1 are as shown in Figure 1.
Film 1 is used for the dehydration of pervaporation ethanol-water system, in 76 DEG C, the ethyl alcohol that material concentration is mass fraction 90%
Under conditions of aqueous solution, permeation flux 1452g/m2H, separation factor 702, as shown in Figure 5.
Embodiment 2 prepares sodium alginate/covalent organic framework composite membrane, and steps are as follows:
9g melamine is dissolved in 300mL dimethyl sulfoxide solvent, 13.5g terephthalaldehyde is then added.180
Argon gas-sealed is vigorously stirred and be passed through at DEG C, after reacting 72h, obtains tan precipitate object.The sediment is successively used into N, N- bis-
It is dried in vacuo for 24 hours after methylformamide and tetrahydrofuran centrifuge washing, obtains yellow powdery solid.The yellow powder is consolidated
Body is placed in Soxhlet extractor, successively respectively extracts 36h using methanol, tetrahydrofuran, methanol at 80 DEG C, product extracted in
It is dried in vacuo at 120 DEG C, obtains covalent organic framework；
It weighs covalent organic framework 0.057g to be dissolved in 25mL deionized water, ultrasonic disperse 15min obtains dispersion liquid.So
0.38g sodium alginate is added in backward dispersion liquid, obtained solution stirs 5h at 30 DEG C with the revolving speed of 300r/min, filter,
It stands, after deaeration, obtains homogeneous casting solution.Casting solution is uniformly spun on polyacrylonitrile ultrafiltration film, drying at room temperature is answered
Close film.Obtained composite membrane is immersed to the CaCl of 0.5M2It is crosslinked in solution, is taken out after 10min, and with a large amount of deionized waters
Flushing membrane calcium ion remained on surface.Composite membrane after crosslinking is dried at room temperature again, finally obtains sodium alginate/covalently have
The section electron microscope of machine skeleton composite membrane (film 2), film 2 is as shown in Figure 2.
Film 2 is used for the dehydration of pervaporation ethanol-water system, in 76 DEG C, the ethyl alcohol that material concentration is mass fraction 90%
Under conditions of aqueous solution, permeation flux 1738g/m2H, separation factor 789, as shown in Figure 5.
Embodiment 3 prepares sodium alginate/covalent organic framework composite membrane, and steps are as follows:
12g melamine is dissolved in 300mL dimethyl sulfoxide solvent, 18g terephthalaldehyde is then added.180
Argon gas-sealed is vigorously stirred and be passed through at DEG C, after reacting 96h, obtains tan precipitate object.The sediment is successively used into N, N- bis-
It is dried in vacuo for 24 hours after methylformamide and tetrahydrofuran centrifuge washing, obtains yellow powdery solid.The yellow powder is consolidated
Body is placed in Soxhlet extractor, successively respectively extracts 48h using methanol, tetrahydrofuran, methanol at 80 DEG C, product extracted in
It is dried in vacuo at 120 DEG C, obtains covalent organic framework.
It weighs covalent organic framework 0.097g to be dissolved in 25mL deionized water, ultrasonic disperse 15min obtains dispersion liquid.So
0.38g sodium alginate is added in backward dispersion liquid, obtained solution stirs 6h at 30 DEG C with the revolving speed of 300r/min, filter,
It stands, after deaeration, obtains homogeneous casting solution.Casting solution is uniformly spun on polyacrylonitrile ultrafiltration film, drying at room temperature is answered
Close film.Obtained composite membrane is immersed to the CaCl of 0.5M2It is crosslinked in solution, is taken out after 15min, and with a large amount of deionized waters
Flushing membrane calcium ion remained on surface.Composite membrane after crosslinking is dried at room temperature again, finally obtains sodium alginate/covalently have
The section electron microscope of machine skeleton composite membrane (film 3), film 3 is as shown in Figure 3.
Film 3 is used for the dehydration of pervaporation ethanol-water system, in 76 DEG C, the ethyl alcohol that material concentration is mass fraction 90%
Under conditions of aqueous solution, permeation flux 2397g/m2H, separation factor 1293, as shown in Figure 5.
Comparative example prepares pure sodium alginate film, and steps are as follows:
0.38g sodium alginate is dissolved in 25mL deionized water, obtained solution is at 30 DEG C with the revolving speed of 300r/min
5h is stirred, filtering is stood, after deaeration, obtains homogeneous casting solution.Casting solution is uniformly spun on polyacrylonitrile ultrafiltration film, room
Temperature is dried to obtain composite membrane.Obtained composite membrane is immersed to the CaCl of 0.5M2It is crosslinked in solution, is taken out after 12min, is used in combination
A large amount of deionized water flushing membranes calcium ion remained on surface.Composite membrane after crosslinking is dried at room temperature again, is finally obtained pure
The section electron microscope of sodium alginate film (comparative film), the comparative film is as shown in Figure 4.
The comparative film is used for the dehydration of pervaporation ethanol-water system, is mass fraction 90% in 76 DEG C, material concentration
Under conditions of ethanol water, permeation flux 1521g/m2H, separation factor 329, as shown in Figure 5.
Although above in conjunction with attached drawing, invention has been described, and the invention is not limited to above-mentioned specific implementations
Mode, the above mentioned embodiment is only schematical, rather than restrictive, and those skilled in the art are at this
Under the enlightenment of invention, without deviating from the spirit of the invention, many variations can also be made, these belong to of the invention
Within protection.
Claims (2)
1. a kind of sodium alginate/covalent organic framework composite membrane, which is characterized in that the sodium alginate/covalent organic framework is compound
Film is made of sodium alginate and covalent organic framework 100:5~30 in mass ratio；Wherein, covalent organic framework is by benzene two
Formaldehyde and the melamine polycondensation of 1~1.5:1 in mass ratio form, and the partial size of covalent organic framework is 60~100nm, and aperture is
0.4~0.6nm, the preparation of the covalent organic framework are that melamine is dissolved in dimethyl sulfoxide solvent, form quality
Volumetric concentration is the solution of 0.02~0.04g/mL, then presses and is added into solution to benzene with 1~1.5:1 of melamine mass ratio
Dicarbaldehyde；Argon gas-sealed is vigorously stirred and be passed through at 180 DEG C, is reacted 48~96h, is obtained tan precipitate object；By the precipitating
Object successively with being dried in vacuo for 24 hours after n,N-Dimethylformamide and tetrahydrofuran centrifuge washing, obtains yellow powdery solid；It will
The yellow powdery solid is placed in Soxhlet extractor, 24 are respectively successively extracted using methanol, tetrahydrofuran, methanol at 80 DEG C~
48h, product extracted are dried in vacuo at 120 DEG C, finally obtain covalent organic framework.
2. a kind of preparation method of sodium alginate as described in claim 1/covalent organic framework composite membrane, which is characterized in that
The following steps are included:
Step 1: the preparation of covalent organic framework:
Melamine is dissolved in dimethyl sulfoxide solvent, the solution that mass-volume concentration is 0.02~0.04g/mL is formed,
Then terephthalaldehyde is added into solution by with 1~1.5:1 of melamine mass ratio；It is vigorously stirred and is passed through at 180 DEG C
Argon gas-sealed reacts 48~96h, obtains tan precipitate object；The sediment is successively used into n,N-Dimethylformamide and tetrahydro
It is dried in vacuo after furans centrifuge washing for 24 hours, obtains yellow powdery solid；The yellow powdery solid is placed in Soxhlet extractor
In, 24~48h, product extracted vacuum at 120 DEG C are respectively successively extracted using methanol, tetrahydrofuran, methanol at 80 DEG C
It is dry, finally obtain covalent organic framework；
Step 2: sodium alginate/covalent organic framework composite membrane film forming:
Covalent organic framework made from step 1 is dissolved in deionized water, ultrasonic disperse 15min obtains dispersion liquid；Then will
Dispersion liquid and a certain amount of sodium alginate are mixed to get solution A, wherein the mass ratio 0.05 of covalent organic framework and sodium alginate
~0.3:1, mass fraction of the sodium alginate in solution A are 1.5%；Solution A stirs 4 at 30 DEG C with the revolving speed of 300r/min
~6h, filtering are stood, after deaeration, obtain homogeneous casting solution；
Casting solution is uniformly spun on polyacrylonitrile ultrafiltration film, drying at room temperature obtains composite membrane；Obtained composite membrane is immersed
The CaCl of 0.5M2Be crosslinked in solution, taken out after 5~15min, with a large amount of deionized water flushing membrane calcium remained on surface from
Son；Composite membrane after crosslinking is dried at room temperature again, finally obtains sodium alginate/covalent organic framework composite membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610103809.6A CN105771677B (en) | 2016-02-25 | 2016-02-25 | Sodium alginate/covalent organic framework composite membrane and preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610103809.6A CN105771677B (en) | 2016-02-25 | 2016-02-25 | Sodium alginate/covalent organic framework composite membrane and preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105771677A CN105771677A (en) | 2016-07-20 |
| CN105771677B true CN105771677B (en) | 2019-01-15 |
Family
ID=56403010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610103809.6A Expired - Fee Related CN105771677B (en) | 2016-02-25 | 2016-02-25 | Sodium alginate/covalent organic framework composite membrane and preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105771677B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102220190B1 (en) * | 2019-04-29 | 2021-02-25 | 서울대학교산학협력단 | Separation membrane and method of manufacturing the same |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107129583B (en) * | 2017-05-25 | 2019-11-15 | 西北师范大学 | The synthetic method of porous organic covalent frame material with triazine structure |
| CN107970790B (en) * | 2017-11-30 | 2020-08-18 | 天津大学 | Functionally gradient covalent organic framework membrane, preparation and application |
| CN108380055A (en) * | 2018-02-28 | 2018-08-10 | 天津大学 | The sodium alginate hybridized film of hollow ZIF-8 nano particles filling and preparation and application |
| CN108355613B (en) * | 2018-03-02 | 2021-06-11 | 南京师范大学常州创新发展研究院 | Magnetic covalent organic framework material and preparation method and application thereof |
| CN110787653B (en) * | 2018-08-01 | 2022-10-11 | 孝感市思远新材料科技有限公司 | Composite membrane containing covalent organic framework material and preparation method thereof |
| CN110465210A (en) * | 2019-08-02 | 2019-11-19 | 北京化工大学常州先进材料研究院 | The preparation and application of SNW-1/ polyacrylonitrile nanofiber flexible membrane |
| CN110743376B (en) * | 2019-09-12 | 2021-11-05 | 南京安纳全诺新材料科技有限公司 | PVDF-COF-MOFs ternary matrix mixed film and preparation method thereof |
| CN110698710B (en) * | 2019-09-23 | 2020-09-25 | 北京师范大学 | Method for preparing covalent organic framework material film by quantitative layer-by-layer self-assembly |
| CN110665378A (en) * | 2019-10-31 | 2020-01-10 | 北京工业大学 | Transition metal ion modified covalent organic framework/polymer hybrid membrane, preparation and application |
| CN113122008A (en) * | 2020-01-14 | 2021-07-16 | 欧菲影像技术（广州）有限公司 | Protective film and preparation method and application thereof |
| CN111760474B (en) * | 2020-07-17 | 2022-05-03 | 天津工业大学 | Preparation method of COFs @ HPAN nanofiltration composite membrane |
| CN112337319A (en) * | 2020-10-21 | 2021-02-09 | 天津大学 | Mixed-dimension assembled covalent organic framework composite membrane, preparation and application |
| CN112295422A (en) * | 2020-10-26 | 2021-02-02 | 天津大学 | Calcium alginate-covalent organic framework material nanosheet-hydrolyzed polyacrylonitrile three-layer membrane and preparation and application thereof |
| CN113185726B (en) * | 2021-04-15 | 2022-05-20 | 华中科技大学 | Method for promoting metal coordination covalent organic framework material to disperse in liquid phase |
| CN114570067A (en) * | 2022-02-24 | 2022-06-03 | 福州大学 | COF-F constructed super-hydrophobic fabric membrane and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766272A (en) * | 2011-05-06 | 2012-11-07 | 中国科学院化学研究所 | Porous material and its preparation method |
| CN104014224A (en) * | 2014-05-26 | 2014-09-03 | 浙江师范大学 | Method for separating carbon dioxide from gas mixture |
| CN104801208A (en) * | 2015-04-07 | 2015-07-29 | 天津大学 | Sodium alginate-flaky ZIF-8 hybrid composite membrane, and preparation and application thereof |
| CN104892879A (en) * | 2014-03-04 | 2015-09-09 | 中国科学院大连化学物理研究所 | Method for growing microporous polymer SNW film on alpha-Al2O3 ceramic surface |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2265390A1 (en) * | 1999-03-11 | 2000-09-11 | University Of Waterloo | Novel composite membrane |
-
2016
- 2016-02-25 CN CN201610103809.6A patent/CN105771677B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766272A (en) * | 2011-05-06 | 2012-11-07 | 中国科学院化学研究所 | Porous material and its preparation method |
| CN104892879A (en) * | 2014-03-04 | 2015-09-09 | 中国科学院大连化学物理研究所 | Method for growing microporous polymer SNW film on alpha-Al2O3 ceramic surface |
| CN104014224A (en) * | 2014-05-26 | 2014-09-03 | 浙江师范大学 | Method for separating carbon dioxide from gas mixture |
| CN104801208A (en) * | 2015-04-07 | 2015-07-29 | 天津大学 | Sodium alginate-flaky ZIF-8 hybrid composite membrane, and preparation and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102220190B1 (en) * | 2019-04-29 | 2021-02-25 | 서울대학교산학협력단 | Separation membrane and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105771677A (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105771677B (en) | Sodium alginate/covalent organic framework composite membrane and preparation and application | |
| CN104801208B (en) | Sodium alginate-flaky ZIF-8 hybrid composite membrane, and preparation and application thereof | |
| CN102794117B (en) | Preparation method of silazane-modified silicalite-1 molecular sieve filling silicon rubber composite membrane | |
| CN110026097B (en) | Preparation method of PIM-1@ MOFs/polymer composite pervaporation membrane | |
| CN102294182B (en) | Preparation method of hydrophobic nano mesoporous molecular sieve filling PDMC composite film | |
| CN101905122B (en) | Self-assembly method for high-load inorganic nano particle hybridized organic membrane | |
| CN107970790B (en) | Functionally gradient covalent organic framework membrane, preparation and application | |
| CN104084052B (en) | A kind of preparation method of silicone rubber composite hollow fiber membrane | |
| CN108380055A (en) | The sodium alginate hybridized film of hollow ZIF-8 nano particles filling and preparation and application | |
| CN104138717A (en) | Preparation method for PDMS/PAN pervaporation hollow fiber membrane | |
| CN107698779A (en) | A kind of method of lignin comprehensive utilization | |
| CN104874300B (en) | Chitosan sulfonation carbon molecular sieve hybridization compounding film and preparation and application | |
| CN103263858A (en) | Cross-linking hyperbranched polymer composite nano filtration membrane prepared by one step method in water phase, preparation method and application | |
| CN101259385B (en) | Quaterisation chitosan penetrating and evaporating film, preparation and application thereof | |
| CN113663529A (en) | Novel macrocyclic aromatic hydrocarbon composite nanofiltration membrane and preparation method thereof | |
| CN110152503A (en) | A kind of preparation method for the solvent resistant nanofiltration membrane that graphene oxide is compound with tool microporous polymer certainly | |
| Liu et al. | Separating 2-phenylethanol from aqueous solution by mixed matrix composite membranes based on beta-cyclodextrin metal organic frameworks | |
| CN103007783A (en) | Preparation method of cellulose ether-ethyl orthosilicate pervaporation hybrid membrane | |
| CN101099924B (en) | Method for preparing chitosan/ZSM-5 molecular compound film | |
| CN111036089A (en) | Preparation method of modified PDMS/ZIF pervaporation hybrid membrane | |
| CN101507904A (en) | Composite ultrafiltration membrane and preparation method thereof | |
| CN105903356A (en) | Layer-by-layer self-assembling preparation method for acid-resisting polyelectrolyte compound film | |
| CN103055717B (en) | Preparation method for cellulose ether-sodium alginate-tetraethylortho silicate pervaporation and hybrid membrane | |
| CN104147947A (en) | Preparation method of PDMS/PAN composite hollow fiber membrane | |
| CN105617879B (en) | Pegylation Polyhedral Oligomeric silsesquioxane/sodium alginate hybridization compounding film and preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190115 Termination date: 20200225 |