CN106823854A - A kind of preparation method of polymer-based metal organic backbone hybridized film - Google Patents
A kind of preparation method of polymer-based metal organic backbone hybridized film Download PDFInfo
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- CN106823854A CN106823854A CN201710111316.1A CN201710111316A CN106823854A CN 106823854 A CN106823854 A CN 106823854A CN 201710111316 A CN201710111316 A CN 201710111316A CN 106823854 A CN106823854 A CN 106823854A
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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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
- B01D71/26—Polyalkenes
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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
- B01D71/30—Polyalkenyl halides
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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Abstract
A kind of preparation method of polymer-based metal organic backbone hybridized film, belongs to technical field of membrane separation.Described method is：Polymer-based film is pre-processed, makes its surface negatively charged；Then by the modified metal ion of film immersion positively charged and the aqueous solution of polymer cation, there is chelation in metal ion and polymer, and by electrostatic attraction assembling to polymer film surface；The film of surface-assembled metal ion and cationic polymer is immersed in the oil-phase solution of organic ligand, the 120min of interfacial reaction 10, MOFs crystal is grown in film surface in situ；Then through over cleaning, be dried to obtain polymer-based metal organic backbone hybridized film.The invention provides a kind of preparation method of new polymer-based metal organic backbone hybridized film；The method has preparation condition gentle, simple and easy to apply, it is easy to the advantages of amplifying；Prepared film for Dye Removal, and with excellent separating property and wide application prospect.
Description
Technical field
The present invention relates to UF membrane field, specially a kind of preparation method of polymer-based metal organic backbone hybridized film.
Technical background
Membrane separation technique due to having the advantages that energy-saving and environmental protection, floor space are small, separative efficiency is high, in recent years by wide
General concern and research.Between ultrafiltration and reverse osmosis, separation yardstick is in the range of 1-10nm for the separation accuracy of NF membrane.Nanofiltration
Film has preferable separating effect to high price salt and low-molecular-weight organic matter, has in terms of in-line coagulation, Dye Removal
Wide application prospect.
Polymer nano filter membrane due to low cost, can with continuous prodution the features such as, be successfully applied to above-mentioned field.But
It is that the permeation flux and selectivity of polymer film are conflicting, if it is desired to obtaining selectivity higher it is necessary to improve masking
During casting solution polymer concentration, necessarily cause the flux of film forming to decline；Conversely, it is also to sacrifice selectivity to improve flux
It is cost.Therefore it how is kept while membrane flux is improved has selectivity higher, is always polymer film research
Focus and difficult point.
In recent years, metal-organic framework materials (MOFs) have high-specific surface area, controllable aperture and pore morphology structure, height
The advantages of porosity and duct sieve effect, the advantage of uniqueness is shown in separation field.Research shows, in the feelings of identical retention
Under condition, the flux of MOFs films can improve 3-10 times than straight polymer film.Therefore by the high selection permeability of MOFs films be polymerized
The processing of thing film and combined using Dominant Facies, be the effective way for preparing high flux and high-selectivity composite nanofiltration membrane.
The invention provides a kind of preparation method of new polymers Base Metal organic backbone hybridized film, in the system of composite membrane
By electrostatic assembly during standby, metal ion and cationic polymer are assembled into membrane surface, recycle interfacial reaction reality
Existing MOFs crystal, so as to increased the specific surface area of film, improves separative efficiency in the three dimensional growth on film surface, is ground with higher
Study carefully value and application prospect.
The content of the invention
The purpose of the present invention is, for existing composite nanometer filtering film, or there are problems that flux is low or rejection is low, invention
A kind of preparation process is simple, the polymer-based metal organic backbone hybridized film with high flux and selectivity.
In order to solve the above problems, the present invention provides a kind of preparation method of polymer-based metal organic backbone hybridized film,
Main technical schemes are as follows：
In the preparation of metal organic framework hybridized film of the invention, make its surface negatively charged polymer matrix membrane modifying, so
Metal ion and polymer cation are deposited into electronegative polymer film surface by electrostatic assembly afterwards；Then boundary is passed through again
Face is reacted, and MOFs hydridization separating layers are grown in polymer-based film surface in situ, and then it is miscellaneous to constitute polymer-based metal organic backbone
Change film.The film of preparation is a kind of high surface, the infiltrative polymer-based metal organic backbone hybridized film of high selection.
The preparation method comprises the following steps：
(1) surface of polymer-based film is modified
(such as chemical graft, plasma irradiation, hydrolysis) is pre-processed to polymer-based film, is made polymer-based film table
Face is negatively charged；The residual agent on film surface is cleaned after treatment with deionized water；
(2) metal ion and cationic polymer are assembled
Polymer-based film obtained by step (1) is immersed in the mixed aqueous solution of metal ion and cationic polymer,
Soaking at room temperature 0.5-20h so that the surface-assembled layer of metal ion/cationic polymer hybrid layer of film, then outwells film table
The unnecessary aqueous solution in face, the water droplet on film surface is dried with filter paper；
(3) interfacial reaction
Film obtained by step (2) is placed in 10-120min in the oil-phase solution of organic ligand, metal ion and organic ligand
One layer of MOFs/ cationic polymer hydridization separating layer is formed in the interfacial reaction growth in situ of water phase and an oil phase；
(4) clean
By film obtained by step (3), cleaned with ethanol, then deionized water cleans film surface, unreacted to remove
Metal ion, organic ligand and residual solvent；
(5) dry
MOFs/ cationic polymer hybridized films obtained in step (4) are dried into 1-2h at room temperature, the film for obtaining is put into modeling
It is standby in envelope.
Described polymer-based film in step (1) is milipore filter or microfiltration membranes, and membrane material is polyacrylonitrile, polychlorostyrene second
Alkene, Kynoar, polyethylene etc., described polymer-based film can be Flat Membrane, hollow-fibre membrane or tubular membrane；
Metal ion in step (2) is the metal ion that can form MOFs materials, such as Zn2+、Co2+、Cu2+Deng metal
Ion concentration is 0.1-1mol/L；Cationic polymer is can be chelated with above-mentioned metal ion containing N or/and O
Cationic polymer, such as polyethyleneimine, sodium alginate, shitosan, polylysine；Cationic polymer is in aqueous
Mass fraction be 0.1-3.0wt.%；
Metal ion in step (2) can form coordination with the cationic polymer containing nitrogen, oxygen by chelation
Metal ion-cationic polymer.
Organic ligand in step (3) is the monomer that MOFs materials can be formed with metal ion, such as imidazoles, pyridine, is had
The concentration of machine part is 0.1-5mol/L, and organic solvent is n-hexane, normal heptane etc..
Reaction temperature in step (3) of the present invention is generally 10-30 DEG C, more preferably preferably 15-25 DEG C, 20 DEG C.
Technical advantage
1st, the diffusion control principle of the chelation and interfacial reaction of bind metal ion and cationic polymer, poly-
Compound membrane surface forms one layer of porous MOFs separating layer, so that the defect of the membrane surface that healed automatically, and realize MOFs
The oriented growth in water-oil two-phase interface, polymer-based metal organic backbone hybridized film surface formed erect sheet overlap
Aspect.
2nd, prepared MOF separating layers have porosity and specific surface area high, and then improve the logical of hybridized film simultaneously
Amount and selectivity, overcome the limitation between traditional polymer membrane flux-selectivity.
3rd, the preparation method is simple and easy to apply, mild condition, it is easy to amplify, for polymer-based metal organic backbone hybridized film
Compound exploitation is significant.
The present invention is described in further detail below in conjunction with brief description of the drawings and specific embodiment.
Brief description of the drawings
Fig. 1 is the schematic diagram of step 4 metal ion and polyethyleneimine generation chelation in the embodiment of the present invention 1；
Interfacial reactions of the Fig. 2 described in step 6 in the embodiment of the present invention 1 forms the schematic diagram of MOFs hybridized films；
Fig. 3 is polymer-based metal organic backbone hybridized film surface scan electromicroscopic photograph prepared by the embodiment of the present invention 1；
Fig. 4 prepares polymer-based metal organic backbone hybridized film profile scanning electromicroscopic photograph for the embodiment of the present invention 1.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment, the present invention is expanded on further.But the present invention is not limited to following examples.
Polymer matrix MOFs hybridized films prepared by the present invention are used for Dye Removal, and the flux and rejection of film are to evaluate
Two important indicators of MOFs hybridized films.
The definition of flux (J) is：(△ t (h)) is through per membrane area (A (m in unit interval2)) water volume (△ V
(L)) as shown in formula (1)；
The definition of rejection is：The ratio between the dye strength and the dye strength of material liquid that are rejected by (formula (2)), wherein
Cf(mol/L) it is material liquid dye strength, Cp(mol/L) it is the dye strength of permeate.
Embodiment 1
The first step, by the sodium hydroxide solution of polyacrylonitrile basement membrane immersion 2mol/L, 1h, polyacrylonitrile is hydrolyzed in 65 DEG C
Middle generation hydrolysis, itrile group is converted into carboxyl, makes film surface negatively charged；
Second step, the polyacrylonitrile (HPAN) after the hydrolysis of step one gained is rinsed repeatedly with deionized water, then will
24h is soaked in gained HPAN films immersion deionized water；
3rd step, configures the zinc nitrate (Zn (NO of 0.2mol/L3)2) aqueous solution, and 0.4wt.% polyethyleneimine
(PEI) aqueous solution, and the two isometric mixing is made into aqueous phase solution；2-methylimidazole/the n-hexane for configuring 0.2mol/L is molten
Liquid is oil-phase solution；
4th step, the Zn (NO that the HPAN films immersion step 3 obtained by step 2 is configured3)2With the mixed aqueous solution of PEI
Middle 1h, Zn2+There is chelation by Zn-N keys with cationic polymer (PEI), and be assembled in by electrostatic interaction negatively charged
HPAN films surface；
5th step, outwells aqueous phase solution, is dried with filter paper and dries film surface residual moisture；
6th step, pours into 2-methylimidazole hexane solution above film obtained by step 5, and interfacial reaction 30min makes
Obtain the Zn on film surface2+With 2-methylimidazole water phase and an oil phase interracial contact, growth in situ forms ZIF-8/PEI hydridization and separates
Layer；
7th step, after reaction, the hexane solution on film surface is outwelled, and film surface residual solvent is cleaned with ethanol and is matched somebody with somebody
Body, then with deionization flushing membrane surface；
8th step, by prepared film as in closed dust-free vent cabinet, drying at room temperature 2h；
MOFs hybridized film NF membranes prepared by the present embodiment, the at 0.2 mpa Congo red aqueous solution for 100mg/L
Cross-flow filtration is carried out, permeation flux is 550.8Lm-2·h-1·MPa-1, rejection is 99%.
Embodiment 2
The interfacial reaction time of step 6 in embodiment 1 is adjusted to 60min, remaining condition is with embodiment 1.Prepared
MOFs hybridized film NF membranes, the Congo red aqueous solution for 100mg/L carries out cross-flow filtration, and permeation flux is 450.8Lm-2·
h-1·MPa-1, rejection is 99.5%.
Embodiment 3
By Zn (NO in step 3 in embodiment 13)2Water-soluble concentration is adjusted to 0.25mol/L, and 2-methylimidazole/n-hexane is molten
Liquid concentration is adjusted to 0.25mol/L；Remaining condition is with embodiment 1.Prepared MOFs hybridized film NF membranes, for 100mg/L
The Congo red aqueous solution carry out cross-flow filtration, permeation flux is 750.8Lm-2·h-1·MPa-1, rejection is 99.8%.
Above content is only example of the present invention and explanation, is not intended to limit the invention, all to of the present invention
Embodiment made any modification, replacement or improve etc., belong in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of polymer-based metal organic backbone hybridized film, it is characterised in that make polymer matrix membrane modifying
Its surface is negatively charged, and metal ion and polymer cation then are deposited into electronegative polymer film table by electrostatic assembly
Face；Then MOFs hydridization separating layers are grown, and then constitute polymer matrix in polymer-based film surface in situ by interfacial reaction again
Metal organic framework hybridized film.
2. the preparation method of polymer-based metal organic backbone hybridized film according to claim 1, it is characterised in that including
Following steps；
(1) surface of polymer-based film is modified
Polymer-based film is pre-processed, makes polymer-based film surface negatively charged；Film surface is cleaned after treatment with deionized water
Residual agent；
(2) metal ion and cationic polymer are assembled
Polymer-based film obtained by step (1) is immersed in the mixed aqueous solution of metal ion and cationic polymer, room temperature
Immersion 0.5-20h so that the surface-assembled layer of metal ion/cationic polymer hybrid layer of film, then outwells film surface many
The remaining aqueous solution, the water droplet on film surface is dried with filter paper；
(3) interfacial reaction
Film obtained by step (2) is placed in 10-120min in the oil-phase solution of organic ligand, metal ion and organic ligand are in water
The interfacial reaction growth in situ of oily two-phase forms one layer of MOFs/ cationic polymer hydridization separating layer；
(4) clean
By film obtained by step (3), cleaned with ethanol, then deionized water cleans film surface, to remove unreacted metal
Ion, organic ligand and residual solvent；
(5) dry
MOFs/ cationic polymer hybridized films obtained in step (4) are dried into 1-2h at room temperature, the film for obtaining is put into plastic packaging bag
In it is standby.
3. the preparation method of a kind of polymer-based metal organic backbone hybridized film according to claim 2, it is characterised in that
Polymer-based film described in step (1) is milipore filter or microfiltration membranes, and form membrane is flat, hollow fiber form or tubular type.
4. the preparation method of a kind of polymer-based metal organic backbone hybridized film according to claim 2, it is characterised in that
Membrane material is polyacrylonitrile, polyvinyl chloride, Kynoar, polyethylene in step (1).
5. the preparation method of a kind of polymer-based metal organic backbone hybridized film according to claim 2, it is characterised in that
Metal ion in step (2) is the metal ion that can form MOFs materials, and concentration of metal ions is 0.1-1mol/L；Sun from
Sub- polymer is the cationic polymer that can be chelated with above-mentioned metal ion containing N or/and O；Polymer cation
Mass fraction in aqueous be 0.1-3.0wt.%, metal ion in step (2) passes through chela with cationic polymer
Cooperation is used, and forms the metal ion-cationic polymer of coordination；Step (3) organic ligand is that can be formed with metal ion
The monomer of MOFs materials.
6. the preparation method of a kind of polymer-based metal organic backbone hybridized film according to claim 2, it is characterised in that
Metal ion is selected from Zn2+、Co2+、Cu2+, cationic polymer is selected from polyethyleneimine, sodium alginate, shitosan, poly- bad ammonia
Acid.
7. the preparation method of a kind of polymer-based metal organic backbone hybridized film according to claim 2, it is characterised in that
Organic ligand in step (3) is imidazoles, pyridine.
8. the preparation method of a kind of polymer-based metal organic backbone hybridized film according to claim 2, it is characterised in that
The concentration of organic ligand is 0.1-5mol/L, and solvent is selected from n-hexane, normal heptane.
9. the preparation method of a kind of polymer-based metal organic backbone hybridized film according to claim 2, it is characterised in that
Reaction temperature in step (3) is 10-30 DEG C.
10. a kind of preparation method of polymer-based metal organic backbone hybridized film according to claim 9, its feature exists
In temperature is 15-25 DEG C.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349807A (en) * | 2017-07-20 | 2017-11-17 | 浙江工业大学 | A kind of Fe（BTC）Big flux polyamide nano composite membrane inlayed and its production and use |
| CN107398186A (en) * | 2017-07-11 | 2017-11-28 | 中国科学技术大学 | Metal organic framework separating layer membrane and preparation method thereof |
| CN108816064A (en) * | 2018-06-26 | 2018-11-16 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of the chitosan nano fiber membrane of growth in situ metal-organic framework material |
| CN108970419A (en) * | 2018-06-14 | 2018-12-11 | 青岛大学 | A kind of preparation method of metal-organic framework material/alginate fibre cloth (MOFs/AFC) composite membrane |
| CN109589890A (en) * | 2019-01-11 | 2019-04-09 | 北京机械设备研究所 | A kind of hydrogen peroxide synthesizer and method |
| CN109876681A (en) * | 2019-03-14 | 2019-06-14 | 浙江工业大学 | A kind of high throughput mixed-matrix nanofiltration membrane and preparation method thereof |
| CN110917910A (en) * | 2019-11-20 | 2020-03-27 | 武汉理工大学 | Preparation method of rigid MOF composite membrane for nanofiltration of organic dye |
| CN111135733A (en) * | 2020-01-13 | 2020-05-12 | 北京赛诺膜技术有限公司 | MOFs polymer hollow fiber composite membrane and preparation method thereof |
| CN112876730A (en) * | 2019-11-29 | 2021-06-01 | 中国科学院大连化学物理研究所 | Method for growing MOF (Metal organic framework) film on high-molecular porous film and application of MOF film |
| CN113786741A (en) * | 2021-08-25 | 2021-12-14 | 西湖大学 | Preparation method of coordination polymer composite membrane |
| CN114288881A (en) * | 2021-12-07 | 2022-04-08 | 武汉工程大学 | ZIFs mixed matrix composite nanofiltration membrane as well as preparation method and application thereof |
| CN114425243A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Metal-organic framework material separation membrane and preparation method and application thereof |
| CN114602331A (en) * | 2020-12-07 | 2022-06-10 | 宁波市电力设计院有限公司 | Preparation method and application of polymer-based composite membrane |
| CN117815906A (en) * | 2024-03-04 | 2024-04-05 | 中山大学 | MAF-6 in-situ growth nanofiltration membrane and preparation method and application thereof |
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| CN107398186A (en) * | 2017-07-11 | 2017-11-28 | 中国科学技术大学 | Metal organic framework separating layer membrane and preparation method thereof |
| CN107398186B (en) * | 2017-07-11 | 2020-03-27 | 中国科学技术大学 | Metal organic framework separation layer film and preparation method thereof |
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| CN112876730B (en) * | 2019-11-29 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for growing MOF (Metal organic framework) film on high-molecular porous film and application of MOF film |
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| CN114425243A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Metal-organic framework material separation membrane and preparation method and application thereof |
| CN114425243B (en) * | 2020-10-15 | 2023-05-12 | 中国石油化工股份有限公司 | Metal-organic framework material separation membrane and preparation method and application thereof |
| CN114602331A (en) * | 2020-12-07 | 2022-06-10 | 宁波市电力设计院有限公司 | Preparation method and application of polymer-based composite membrane |
| CN114602331B (en) * | 2020-12-07 | 2023-11-17 | 宁波市电力设计院有限公司 | Preparation method and application of polymer-based composite film |
| CN113786741A (en) * | 2021-08-25 | 2021-12-14 | 西湖大学 | Preparation method of coordination polymer composite membrane |
| CN113786741B (en) * | 2021-08-25 | 2023-02-14 | 西湖大学 | Preparation method of coordination polymer composite membrane |
| CN114288881A (en) * | 2021-12-07 | 2022-04-08 | 武汉工程大学 | ZIFs mixed matrix composite nanofiltration membrane as well as preparation method and application thereof |
| CN117815906A (en) * | 2024-03-04 | 2024-04-05 | 中山大学 | MAF-6 in-situ growth nanofiltration membrane and preparation method and application thereof |
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Application publication date: 20170613 |