CN116328544B - Mixed matrix membrane containing cyclodextrin material and preparation method and application thereof - Google Patents
Mixed matrix membrane containing cyclodextrin material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116328544B CN116328544B CN202310339747.9A CN202310339747A CN116328544B CN 116328544 B CN116328544 B CN 116328544B CN 202310339747 A CN202310339747 A CN 202310339747A CN 116328544 B CN116328544 B CN 116328544B
- Authority
- CN
- China
- Prior art keywords
- cyclodextrin
- gamma
- film
- mixed matrix
- pdms
- 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.)
- Active
Links
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 89
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000012528 membrane Substances 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 238000005266 casting Methods 0.000 claims abstract description 23
- 229920000620 organic polymer Polymers 0.000 claims abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 62
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 62
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 56
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005416 organic matter Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 7
- 238000005373 pervaporation Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000008961 swelling Effects 0.000 abstract description 7
- 239000002033 PVDF binder Substances 0.000 description 21
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 21
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 13
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 13
- -1 polydimethylsiloxane Polymers 0.000 description 9
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 5
- 239000001116 FEMA 4028 Substances 0.000 description 5
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 5
- 229960004853 betadex Drugs 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
Abstract
The invention discloses a mixed matrix membrane containing cyclodextrin and a preparation method and application thereof, belonging to the field of membrane separation. The preparation method of the mixed matrix membrane containing cyclodextrin comprises the steps of mixing a cyclodextrin material (CD) with a hydrophobic organic polymer, a crosslinking agent and a catalyst, so that the hydrophobic organic polymer is crosslinked into a network structure, and the cyclodextrin is connected with the network structure through a hydrogen bond acting force to obtain a casting solution; and (3) crosslinking the casting film liquid on the base film to obtain the mixed matrix film. The invention solves the problems that the membrane separation performance of the hydrophobic organic polymer is reduced due to easy swelling.
Description
Technical Field
The invention belongs to the field of membrane separation, and particularly relates to a mixed matrix membrane containing cyclodextrin materials, and a preparation method and application thereof.
Background
The pervaporation technology is used for separating liquid mixtures, and has the outstanding advantage of being capable of realizing separation tasks which are difficult to complete by traditional methods such as distillation, extraction, absorption and the like with lower energy consumption. It is particularly suitable for separating near-boiling, constant-boiling mixtures and isomers which are difficult or impossible to separate by distillation; the method has obvious technical and economic advantages for removing trace water in the organic solvent and the mixed solvent and separating a small amount of organic pollutants in the wastewater. Therefore, the pervaporation technology has wide application prospect and market in the industrial fields of petrochemical industry, medicine, food, environmental protection and the like. The world academy is called one of the most promising high technologies in the twentieth century.
At present, the pervaporation membrane separation technology at home and abroad has realized large-scale industrialized application in the aspect of removing a small amount of water in an organic solvent. However, the separation of bioethanol from water by pervaporation technology has become a subject of interest to many researchers, in that the removal or recovery of low concentrations of organic matter from water is still in the primary stage of use, particularly as bioenergy is developed.
In the preparation of bioethanol, the concentration of ethanol prepared by fermenting cellulose is low, about 5%, and the ethanol has a product inhibition effect in the fermentation process. In order to improve the conversion rate of the ethanol and reduce the energy consumption of ethanol concentration, a proper separation process needs to be developed, and the traditional rectification process is unfavorable for continuous operation and has higher energy consumption, so that the aim of producing the ethanol with low consumption and high efficiency can be fulfilled if the high-performance priority alcohol permeable membrane can be prepared.
For the alcohol-permeable membrane, researchers have proposed the concept of an organic-inorganic hybrid membrane, and have conducted studies on the combination of an organic polymer membrane material and inorganic particles to improve the separation effect of the hybrid membrane. However, the adhesion between the inorganic particles and the organic polymer membrane material is very weak, so that the compatibility of the inorganic particles and the organic polymer membrane material is poor, defects are easily generated on the manufactured membrane structure, compared with the traditional inorganic nanoparticles, the organic nanoparticle cyclodextrin and the polymer material have stronger compatibility, and a large number of hydroxyl groups in cyclodextrin molecules can enhance the separation performance and mechanical performance of the organic polymer membrane with the organic polymer molecules through intermolecular force, and meanwhile, the swelling resistance of the membrane is improved.
Disclosure of Invention
The invention solves the technical problem of poor swelling resistance in the mixed matrix membrane in the prior art.
In a first aspect, the present invention provides a method for preparing a mixed matrix film comprising a cyclodextrin material, comprising the steps of:
s1: dissolving cyclodextrin in an organic solvent to obtain a solution A; mixing the solution A, a hydrophobic organic polymer, a cross-linking agent and a catalyst to crosslink the hydrophobic organic polymer into a network structure, wherein the cyclodextrin is connected with the network structure through a hydrogen bond acting force to obtain a casting solution;
s2: pouring the casting solution in the step S1 on the surface of a base film, and crosslinking for 5-10 hours at the temperature of 30-100 ℃ to crosslink the casting solution and the base film; after the organic solvent in the casting film liquid volatilizes, a cross-linked layer containing cyclodextrin material is formed on the surface of the base film, and the cross-linked layer and the base film jointly form a mixed matrix film.
Preferably, the cyclodextrin in step S1 is one of α -cyclodextrin, β -cyclodextrin or γ -cyclodextrin.
Preferably, the hydrophobic organic polymer in the step S1 is polydimethylsiloxane or polymethylphenylsiloxane; the cross-linking agent in the step S1 is tetraethoxysilane, phenyl triethoxysilane, methyl triethoxysilane or tetramethoxysilane; the catalyst in the step S1 is dibutyl tin dilaurate.
Preferably, the base film in step S2 is a polymer base film;
preferably, the polymer-based membrane is a polysulfone-based membrane, a polyethersulfone-based membrane, a polyvinylidene fluoride-based membrane, or a polyacrylonitrile-based membrane.
Preferably, in the step S1, the mass ratio of the cyclodextrin material, the hydrophobic organic polymer, the crosslinking agent and the catalyst in the solution a is (0.1-1): 10:1:0.05.
preferably, the cyclodextrin is present in an amount of 1wt% to 10wt%, preferably 5wt%, based on the mass of the mixed matrix film.
According to a second aspect of the present invention, there is provided a mixed matrix membrane comprising cyclodextrin material prepared by the above-described preparation method.
According to a third aspect of the present invention there is provided the use of a mixed matrix membrane comprising a cyclodextrin material as described above for membrane separation.
Preferably, the mixed matrix membrane containing cyclodextrin material is used for separating organic matter from a mixture of organic matter dissolved in water;
preferably, the organic matter is organic alcohol or aniline organic matter;
preferably, the organic alcohol is at least one of methanol, ethanol, n-propanol, allyl alcohol and n-butanol; the aniline organic matter is at least one of aniline, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine.
The invention has the following advantages:
(1) According to the invention, the compatibility with the hydrophobic organic polymer and the membrane separation performance are improved by adding the organic Cyclodextrin (CD) nano particles, and the obtained mixed matrix membrane has the advantages of large permeation flux, high selectivity, good compatibility with high molecules and difficult agglomeration.
(2) The invention preferably connects the large-hole gamma-cyclodextrin (gamma-CD) material with the dimethyl siloxane (PDMS) crosslinked into a network structure through hydrogen bonds, and the hydroxyl groups of the gamma-cyclodextrin (gamma-CD) material containing hydroxyl groups can form hydrogen bonds with oxygen atoms in the PDMS due to the hydrophobicity of the PDMS, so that the swelling resistance of the gamma-cyclodextrin (gamma-CD)/PDMS film is better than that of the PDMS, and meanwhile, the holes of the gamma-cyclodextrin (gamma-CD) are larger than the size of organic molecules, so that the organic molecules can quickly pass through in the separation process, the diffusion resistance is reduced, and the separation performance of the mixed matrix film for separating the organic solvent from the mixed solvent after the organic solvent and water are mutually dissolved is effectively improved by utilizing the gamma-cyclodextrin (gamma-CD) material containing the hydroxyl groups.
(3) According to the invention, the cyclodextrin containing hydroxyl is crosslinked with the hydrophobic organic polymer to form a film, preferably mixed with Polydimethylsiloxane (PDMS), so that the problem of swelling resistance of PDMS is solved, and the separation performance of the Cyclodextrin (CD)/PDMS mixed matrix film is improved.
The preparation method of the mixed matrix membrane containing the cyclodextrin material is simple and easy to implement, and has potential application prospect.
Drawings
FIG. 1 is an infrared spectrum of PDMS, gamma-CD and gamma-CD/PDMS.
FIG. 2 shows the static water contact angles of gamma-CD/PDMS/PVDF and PDMS/PVDF at different levels.
FIG. 3 shows permeation flux and separation factor for different levels of gamma-CD/PDMS/PVDF mixed matrix membranes.
FIG. 4 shows PDMS/PVDF and gamma-CD/PDMS/PVDF-5 wt% long term performance.
FIG. 5 is a SEM image of the surface of a mixed matrix membrane of PDMS/PVDF and gamma-CD/PDMS/PVDF at different levels.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention provides a preparation method of a mixed matrix membrane containing cyclodextrin, which comprises the following steps:
s1: dissolving cyclodextrin in an organic solvent to obtain a solution A; mixing the solution A, a hydrophobic organic polymer, a cross-linking agent and a catalyst to crosslink the hydrophobic organic polymer into a network structure, wherein the cyclodextrin is connected with the network structure through a hydrogen bond acting force to obtain a casting solution;
s2: pouring the casting solution in the step S1 on the surface of a base film, and crosslinking for 5-10 hours at the temperature of 30-100 ℃ to crosslink the casting solution and the base film; after the organic solvent in the casting film liquid volatilizes, a cross-linked layer containing cyclodextrin material is formed on the surface of the base film, and the cross-linked layer and the base film jointly form a mixed matrix film.
In step S1, the cyclodextrin is one of alpha-cyclodextrin (alpha-CD), beta-cyclodextrin (beta-CD) or gamma-cyclodextrin (gamma-CD), preferably gamma-cyclodextrin.
In step S1, cyclodextrin: polydimethylsiloxane (PDMS): crosslinking agent: catalyst= (0.1-1): 10:1:0.05, preferably 0.5:10:1:0.05
In step S2, the polymer base film may be Polysulfone (PSF), polyethersulfone (PES), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), or the like, and PVDF is preferable.
In step S2, the crosslinking time of PDMS and the base film is 5-10h, preferably 6h, the thermal crosslinking temperature is 30-100deg.C, preferably 80 ℃.
Example 1:
in a 250mL round bottom flask, raw materials containing alpha-cyclodextrin (alpha-CD), polydimethylsiloxane (PDMS), a cross-linking agent and a catalyst are mixed according to the mass ratio of 0.5:10:1:0.05 to form casting solution, after the casting solution is stirred uniformly, the vacuum is defoamed for 2 hours, finally the casting solution is poured on a prepared PVDF base film, the film is scraped by a scraper, and then the film is placed in an oven for cross-linking for 5 hours at 60 ℃.
Example 2:
in a 250mL round bottom flask, raw materials containing beta-cyclodextrin (beta-CD), polymethylphenylsiloxane (PMPS), a cross-linking agent and a catalyst are mixed according to the mass ratio of 0.1:10:1:0.05 to form casting solution, after the casting solution is stirred uniformly, the vacuum is defoamed for 2 hours, finally the casting solution is poured on a prepared polyether sulfone membrane, the membrane is scraped by a scraper, and then the mixture is placed into an oven for cross-linking for 6 hours at 50 ℃.
Example 3:
in a 250mL round bottom flask, raw materials containing gamma-cyclodextrin (gamma-CD), polydimethylsiloxane (PDMS), a cross-linking agent and a catalyst are mixed according to the mass ratio of 0.5:10:1:0.05 to form casting solution, after the casting solution is stirred uniformly, vacuum defoaming is carried out for 2 hours, finally the casting solution is poured on a prepared polyacrylonitrile-based film, the film is scraped by a scraper, and then the film is placed in an oven for cross-linking for 8 hours at 70 ℃.
FIG. 1 is an infrared spectrum of PDMS, gamma-CD and gamma-CD/PDMS. It can be seen from the figure that the addition of gamma-CD did not cause a change in PDMS functionality.
FIG. 2 shows the static water contact angles of gamma-CD/PDMS/PVDF and PDMS/PVDF at different levels. As the amount of gamma-CD increases, the hydrophobicity of gamma-CD/PDMS/PVDF increases and then decreases, and the hydrophobic property reaches a maximum at a content of 5wt%, which may be related to a change in the roughness of the film surface, and in the range of 0 to 5wt%, the addition of gamma-CD increases the roughness of the film, and when the content exceeds 5wt%, the addition of gamma-CD decreases the roughness of the film.
FIG. 3 shows permeation flux and separation factor for different levels of gamma-CD/PDMS/PVDF mixed matrix membranes. The permeation flux and the separation factor are increased and then decreased with the content, and reach the maximum value at the content of 5wt%, which shows that the gamma-CD/PDMS/PVDF mixed matrix membrane overcomes the trade-off effect.
FIG. 4 shows PDMS/PVDF and gamma-CD/PDMS/PVDF-5 wt% long term performance. From the figure, it can be seen that the PDMS/PVDF membrane flux and separation effect is slowly reduced, while the long-term running performance of gamma-CD/PDMS/PVDF-5 wt% is basically unchanged, which is probably that the addition of gamma-CD improves the swelling resistance of the original PDMS/PVDF membrane, thereby improving the long-term running performance and the service life of the membrane.
FIG. 5 is a SEM image of the surface of a mixed matrix membrane of PDMS/PVDF and gamma-CD/PDMS/PVDF at different levels. It can be seen from the figure that the gamma-CD content is more than 5wt% and the gamma-CD is agglomerated, resulting in a poorer separation than gamma-CD/PDMS/PVDF-5 wt%.
TABLE 1 Properties of Cyclodextrin/PDMS pervaporation Membrane separation of aqueous 5wt% ethanol
| Film material | Filling material | Mass fraction (wt%) | Flux (g/m) 2 h) | Separation factor |
| PDMS | ____ | ____ | 473 | 5.1 |
| α-CD/PDMS | α-CD | 3 | 588 | 6.4 |
| α-CD/PDMS | α-CD | 5 | 797 | 8.6 |
| α-CD/PDMS | α-CD | 7 | 665 | 7.4 |
| α-CD/PDMS | α-CD | 10 | 574 | 5.8 |
| β-CD/PDMS | β-CD | 3 | 614 | 6.2 |
| β-CD/PDMS | β-CD | 5 | 848 | 9.2 |
| β-CD/PDMS | β-CD | 7 | 701 | 7.7 |
| β-CD/PDMS | β-CD | 10 | 629 | 6.6 |
| γ-CD/PDMS | γ-CD | 3 | 641 | 6.6 |
| γ-CD/PDMS | γ-CD | 5 | 894 | 9.8 |
| γ-CD/PDMS | γ-CD | 7 | 783 | 8.7 |
| γ-CD/PDMS | γ-CD | 10 | 657 | 7.2 |
Table 1 shows the aqueous performance of cyclodextrin/PDMS pervaporation membrane separation of 5wt% ethanol. From the figure, it can be seen that the separation performance of the gamma-CD/PDMS/PVDF-5 wt% film is the best, probably because the compatibility and acting force between gamma-CD molecules and PDMS are enhanced through intermolecular hydrogen bonds, so that the mobility of PDMS after absorbing the organic solvent is weakened, and the swelling performance of the film is reduced.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (4)
1. A method for preparing a mixed matrix film comprising a cyclodextrin material, comprising the steps of:
s1: dissolving gamma-cyclodextrin in an organic solvent to obtain a solution A; mixing the solution A, a hydrophobic organic polymer, a cross-linking agent and a catalyst to crosslink the hydrophobic organic polymer into a network structure, wherein the gamma-cyclodextrin is connected with the network structure through a hydrogen bond acting force to obtain a casting solution;
s2: pouring the casting solution in the step S1 on the surface of a base film, and crosslinking for 5-10 hours at the temperature of 30-100 ℃ to crosslink the casting solution and the base film; after the organic solvent in the casting film liquid volatilizes, a cross-linking layer containing a gamma-cyclodextrin material is formed on the surface of the base film, and the cross-linking layer and the base film jointly form a mixed matrix film, wherein in the gamma-cyclodextrin/PDMS film, the mass fraction of the gamma-cyclodextrin is 5%, the gamma-cyclodextrin/PDMS pervaporation film separates an aqueous solution of 5wt% ethanol, and the flux is 894g/m 2 h, the separation factor is as high as 9.8.
2. The mixed matrix membrane containing a gamma-cyclodextrin material prepared by the method for preparing a mixed matrix membrane containing a cyclodextrin material according to claim 1.
3. Use of a mixed matrix membrane comprising a cyclodextrin material as defined in claim 2 for membrane separation.
4. Use according to claim 3 for separating organic matter from a mixture of organic matter dissolved in water;
the organic matter is organic alcohol or aniline organic matter;
the organic alcohol is at least one of methanol, ethanol, n-propanol, allyl alcohol and n-butanol; the aniline organic matter is at least one of aniline, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310339747.9A CN116328544B (en) | 2023-03-29 | 2023-03-29 | Mixed matrix membrane containing cyclodextrin material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310339747.9A CN116328544B (en) | 2023-03-29 | 2023-03-29 | Mixed matrix membrane containing cyclodextrin material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116328544A CN116328544A (en) | 2023-06-27 |
| CN116328544B true CN116328544B (en) | 2023-11-21 |
Family
ID=86894732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310339747.9A Active CN116328544B (en) | 2023-03-29 | 2023-03-29 | Mixed matrix membrane containing cyclodextrin material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116328544B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116966759B (en) * | 2023-08-08 | 2024-01-30 | 山东中盛药化设备有限公司 | Preparation method and application of organic framework mixed membrane for VOCs recovery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1363415A (en) * | 2001-12-26 | 2002-08-14 | 天津大学 | Process for preparing osmosizing and evaporating polycyclodextrin-silica gel membrane for removing VOCs |
| JP2003093852A (en) * | 2001-09-25 | 2003-04-02 | Sangaku Renkei Kiko Kyushu:Kk | Method for producing separation membrane and separation membrane forming material and separation membrane obtained thereby |
| CN104128102A (en) * | 2014-08-04 | 2014-11-05 | 郑州大学 | Cyclodextrin modified composite organic solvent nanofiltration membrane and preparation method thereof |
| CN104624062A (en) * | 2015-01-23 | 2015-05-20 | 中国石油大学(华东) | Polydimethylsiloxane/polyvinylidene fluoride composite film and preparation method thereof |
| CN105879720A (en) * | 2014-12-16 | 2016-08-24 | 江南大学 | Preparation method of heat and chemical cross-linked hyperbranched polysiloxane pervaporation membrane |
| CN106606930A (en) * | 2016-12-30 | 2017-05-03 | 南京悠谷知识产权服务有限公司 | Magnetic hydrophobic membrane and preparation method thereof, and method for recovering VOCs (volatile organic compounds) from filling station |
| CN114163817A (en) * | 2021-11-10 | 2022-03-11 | 浙江大学 | Slow-release antibacterial film and preparation method thereof |
| CN114377557A (en) * | 2022-01-24 | 2022-04-22 | 宁波巨化化工科技有限公司 | Clean production process for continuously preparing n-propanol |
| WO2022254032A1 (en) * | 2021-06-03 | 2022-12-08 | Aquaporin A/S | Plant-derived vesicles incorporating trans-membrane proteins |
-
2023
- 2023-03-29 CN CN202310339747.9A patent/CN116328544B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003093852A (en) * | 2001-09-25 | 2003-04-02 | Sangaku Renkei Kiko Kyushu:Kk | Method for producing separation membrane and separation membrane forming material and separation membrane obtained thereby |
| CN1363415A (en) * | 2001-12-26 | 2002-08-14 | 天津大学 | Process for preparing osmosizing and evaporating polycyclodextrin-silica gel membrane for removing VOCs |
| CN104128102A (en) * | 2014-08-04 | 2014-11-05 | 郑州大学 | Cyclodextrin modified composite organic solvent nanofiltration membrane and preparation method thereof |
| CN105879720A (en) * | 2014-12-16 | 2016-08-24 | 江南大学 | Preparation method of heat and chemical cross-linked hyperbranched polysiloxane pervaporation membrane |
| CN104624062A (en) * | 2015-01-23 | 2015-05-20 | 中国石油大学(华东) | Polydimethylsiloxane/polyvinylidene fluoride composite film and preparation method thereof |
| CN106606930A (en) * | 2016-12-30 | 2017-05-03 | 南京悠谷知识产权服务有限公司 | Magnetic hydrophobic membrane and preparation method thereof, and method for recovering VOCs (volatile organic compounds) from filling station |
| WO2022254032A1 (en) * | 2021-06-03 | 2022-12-08 | Aquaporin A/S | Plant-derived vesicles incorporating trans-membrane proteins |
| CN114163817A (en) * | 2021-11-10 | 2022-03-11 | 浙江大学 | Slow-release antibacterial film and preparation method thereof |
| CN114377557A (en) * | 2022-01-24 | 2022-04-22 | 宁波巨化化工科技有限公司 | Clean production process for continuously preparing n-propanol |
Non-Patent Citations (4)
| Title |
|---|
| Functionalization of polymeric membranes by impregnation and in situ cross-linking of a PDMS/β-cyclodextrin network;Fontananova, E, et.al;Journal of Inclusion Phenomena and Macrocyclic Chemistry;第57卷(第1-4期);537-543 * |
| PDMS渗透蒸发膜的制备及其处理含酚废水的研究;马克;中国优秀硕士学位论文全文数据库(第8期);1-87 * |
| 含环糊精膜的制备与应用;周志军等;化学进展;第19卷(第9期);1436-1442 * |
| 聚环糊精填充PDMS渗透蒸发膜分离苯酚水溶液;方志平等;化工学报;第57卷(第4期);843-848 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116328544A (en) | 2023-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bandehali et al. | New mixed matrix PEI nanofiltration membrane decorated by glycidyl-POSS functionalized graphene oxide nanoplates with enhanced separation and antifouling behaviour: Heavy metal ions removal | |
| Liu et al. | A novel PVDF/PFSA-g-GO ultrafiltration membrane with enhanced permeation and antifouling performances | |
| Xue et al. | High-flux nanofiltration membranes prepared with β-cyclodextrin and graphene quantum dots | |
| CN102327746B (en) | Anti-pollution cyclodextrin-polymer composite nano-filtration membrane and preparation method thereof | |
| CN116328544B (en) | Mixed matrix membrane containing cyclodextrin material and preparation method and application thereof | |
| Chen et al. | Preparation of mixed matrix composite membrane for hydrogen purification by incorporating ZIF-8 nanoparticles modified with tannic acid | |
| CN110026097B (en) | Preparation method of PIM-1@ MOFs/polymer composite pervaporation membrane | |
| Si et al. | A high-efficiency diffusion process in carbonized ZIF-8 incorporated mixed matrix membrane for n-butanol recovery | |
| Ren et al. | CF3-MOF enhanced pervaporation selectivity of PDMS membranes for butanol separation | |
| Wong et al. | Highly permeable and selective graphene oxide-enabled thin film nanocomposite for carbon dioxide separation | |
| CN105214502A (en) | A kind of Nano Silver/Graphene/polyvinyl alcohol mixing matrix membrane and preparation method thereof | |
| CN103657456A (en) | Preparation method of ethanol-permselective POSS (polyhedral oligomeric silsesquioxanes)/silicone rubber composite membrane | |
| CN111450717A (en) | High-performance polymer organic solvent nanofiltration membrane and preparation method thereof | |
| Lecaros et al. | Tannin-based thin-film composite membranes integrated with nitrogen-doped graphene quantum dots for butanol dehydration through pervaporation | |
| Lecaros et al. | Ionically cross-linked sodium alginate and polyamidoamine dendrimers for ethanol/water separation through pervaporation | |
| CN113509847A (en) | Method for preparing porous nano particle/polydimethylsiloxane membrane by spreading on water surface | |
| Peng et al. | Modified silica incorporating into PDMS polymeric membranes for bioethanol selection | |
| CN112316741B (en) | Mixed matrix membrane of beaded MOF filled silicone rubber | |
| Atazadeh et al. | Synthesis of PMHS–PDMS composite membranes embedded with silica nanoparticles and their application to separate of DMSO from aqueous solutions | |
| CN108126534B (en) | APTS modified carbon black filled PIM-1 composite membrane, preparation method thereof and method for separating and purifying n-butyl alcohol | |
| CN108031301B (en) | MAPS modified silicon dioxide filled PIM-1 composite membrane and preparation method thereof | |
| Pan et al. | Enhanced water-selective performance of dual-layer hybrid membranes by incorporating carbon nanotubes | |
| Zhao et al. | Designing high-performance pervaporation membranes with hierarchical hydrophobic-hydrophilic coating layers | |
| CN108554203B (en) | HDTMS modified silicon dioxide filled PIM-1 composite membrane and preparation method thereof | |
| Ren et al. | Interfacial polymerization process based on diffusion control: Role of chemical composition and morphology on fouling resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |