CN109021264A - A kind of preparation method of MOFs- chitosan nano fiber composite membrane - Google Patents
A kind of preparation method of MOFs- chitosan nano fiber composite membrane Download PDFInfo
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Abstract
The invention belongs to the technical field of high molecular material preparation, specifically a kind of preparation methods of MOFs- chitosan nano fiber composite membrane.Chitosan nano fiber is prepared by method of electrostatic spinning, it is then, compound under crosslinking action after the MOFs material of synthesis is blended with chitosan nano fiber, obtain MOFs- chitosan nano fiber composite membrane.The present invention efficiently solves that the compound film-strength of MOFs- chitosan nano fiber is low, stability is poor and MOFs material the problems such as bad dispersibility, has been prepared with high MOFs retention, high intensity and excellent water-fast and solvent resistance MOFs- chitosan nano fiber composite membrane in chitin fiber.Meanwhile should preparation method is simple, preparation condition is mild, be suitble to large-scale production, be expected to expand application of the composite membrane in the fields such as Dye Adsorption, adsorption of metal ions, gas absorption and storage.
Description
Technical field
The invention belongs to the technical field of high molecular material preparation, specifically a kind of MOFs- chitosan nano fibers
The preparation method of composite membrane.
Background technique
Chitosan (Chitosan) is the natural cationic polymer being widely present in nature, have it is cheap, nontoxic, can
The advantages that biodegrade, good film-forming property, be the renewable resource second largest in the world for being only second to cellulose.Chitin fiber is usual
Be using chitin after concentrated base processing removing acetyl group by fiber made by wet spinning, absorbability suture,
The medicine and hygiene fields such as hemostatic cotton, artificial dialysis film, artificial skin, tissue stent material and dressing have a wide range of applications.
It (is fragrant polyacid and more mostly that metal organic frame (MOFs) material, which is by the multiple tooth organic ligand of oxygen-containing, nitrogen etc.,
Alkali) with transition metal ions self assembly made of coordination polymer.MOFs is as a kind of extremely-low density porous material, in gas
Absorption has wider application prospect with storage, Dye Adsorption etc..But MOFs insufficient formability, by MOFs and other high scores
Sub- material is mixed with the main means that composite material is its application.
Currently, the surface that chitosan is blended to preparation with MOFs (MIL-101) has the nanofiltration membrane of positive charge, it to be used for multivalence
The removal of cation has achieved preferable effect (Journal of Membrane Science, 2017,525:269-276).
Meanwhile preparation is blended with MOFs (CPO-27-Ni) in chitosan, and there is the microballoon of superhigh specific surface area also to have been reported that
(Chemistry,2014,20,8973-8978).In addition, loading MOFs for chitosan as skeleton, can be used after being carbonized
In the positive electrode (Chemical Communications, 2014,50 (59): 8057-8060) of lithium battery.However, system is blended
There is MOFs and chitosan binding strengths that poor, MOFs is easy to fall off for standby MOFs- chitosan material, and MOFs is poly- in shell
In sugar juice the disadvantages of bad dispersibility, meanwhile, the report being blended at this stage without chitosan nano fiber with MOFs.
Summary of the invention
The object of the present invention is to provide a kind of methods of MOFs- chitosan nano fiber composite membrane.
To achieve the above object, the invention adopts a technical scheme as:
A kind of preparation method of MOFs- chitosan nano fiber composite membrane, is prepared chitosan by method of electrostatic spinning
Nanofiber, it is then, compound under crosslinking action after the MOFs material of synthesis is blended with chitosan nano fiber, it obtains
MOFs- chitosan nano fiber composite membrane.
The MOFs material be dissolved in organic solvent with chitosan nano fiber be blended dispersion after crosslinking agent is added, after reaction
Filtering, organic solvent washing, obtain MOFs- chitosan nano fiber composite membrane；The organic solvent be methanol or dehydrated alcohol,
The organic solvent and chitosan nano fiber volume mass (mL/g) ratio are 50-500:1.
Wherein, MOFs material and chitosan nano fiber can be dissolved in organic solvent simultaneously, can also be dissolved in respectively organic molten
In agent；
The crosslinking agent is glutaraldehyde, glyoxal, formaldehyde, silane coupling agent, inorganic crosslinking agent, amino resins, phenolic aldehyde tree
Rouge, epoxy resin are one such or several, and dosage is the 0.1%-20% of chitosan nano fiber quality, preferred crosslinking agent
For glutaraldehyde or glyoxal and epoxychloropropane, preferable amount is the 1%-10% of chitosan nano fiber quality.
The crosslinking process is that 0.5h-5h, preferably 100r/min- are stirred under 50r/min-1000r/min rate
1h-3h is stirred under 500r/min.
The chitosan nano fiber be by chitosan be raw material by electrostatic spinning in a manner of the diameter that obtains be less than 200nm
Fiber.
The chitosan nano fiber be by chitosan be raw material by wet electrostatic spinning in a manner of prepare, by shell
Glycan and polyethylene glycol oxide are respectively added slowly in concentrated acid solution, water is added after mixing obtains uniformly sticky chitosan and wait spinning
Solution carries out electrostatic spinning after being then ultrasonically treated, and chitin fiber is obtained after removing；Wherein, in chitosan solution to be spun
The final concentration of 1%-10% of acid, chitosan account for the 0.5%-5% of acid solution quality, and polyethylene glycol oxide accounts for acid solution quality
0.1%-10%.
Preferably final concentration of 3%-5% sour in chitosan solution to be spun, chitosan account for the 1%- of acid solution quality
3%, polyethylene glycol oxide accounts for the 0.1%-1% of acid solution quality.
After solution ultrasound, solution is extracted with syringe and carries out electrostatic spinning, using tinfoil as receiver board, spinning condition
Are as follows: positive pressure 2.0KV-13.0KV, negative pressure are -5.0KV--10.0KV, and injecting speed is 0.02mm/min-0.15mm/min, are put down
Shifting speed is 100mm/min-500mm/min, and the revolving speed for receiving roller is 5r/min-30r/min.
The MOFs material is made of metal salt and ligand, wherein metal salt refers to major element, transition elements or lanthanum
Series elements are one or more of the water soluble salt of metal cation；Dosage is the 1%- of chitosan nano fiber quality
30%；Ligand refers to one or more of oxygen-containing or nitrogen organic anionic ligands containing carboxyl, or with nitrogen-containing heterocycle it is organic in
Property ligand be used in conjunction with, ligand additional amount be chitosan nano fiber quality 1%-30%.
The metal salt is zinc nitrate, cobalt chloride, copper acetate, chromic nitrate, zirconium chloride or nickel chloride, and dosage is chitosan
The 5%-20% of nanofiber quality；Ligand be 2-methylimidazole, trimesic acid, terephthalic acid (TPA), 2- amino terephthalic acid (TPA),
Terephthalic acid (TPA), dosage are the 5%-20% of chitosan nano fiber quality.
Above-mentioned metal salt can be by existing preparation with dosage relation when ligand formation MOFs material between the two simultaneously
Method carries out, and deploys.
The preparation method of MOFs- chitosan nano fiber composite membrane of the invention has the advantage that
The present invention proposes MOFs is compound with chitosan nano fiber, MOFs and chitosan nano fibre by cross-linking reaction
Bond strength with higher is tieed up, MOFs retention is high, is uniformly dispersed, and it is orderly aligned, so that the MOFs- chitosan nano arrived
Rice composite fiber membrane stability with higher.Preparation method is simple for this, and preparation condition is mild, is suitble to large-scale production,
Obtained composite membrane has excellent water-fast and solvent resistance, and therefore, the composite membrane is in Dye Adsorption and separation of metal ions
Equal directions have potential using value.
The present invention efficiently solves that the compound film-strength of MOFs- chitosan nano fiber is low, stability is poor and MOFs material
In chitin fiber the problems such as bad dispersibility, be prepared with high MOFs retention, high intensity and it is excellent water-fast and
The MOFs- chitosan nano fiber composite membrane of solvent resistance.Meanwhile should preparation method is simple, preparation condition is mild, be suitble to
Large-scale production, is expected to expand the composite membrane answering in the fields such as Dye Adsorption, adsorption of metal ions, gas absorption and storage
With.
Detailed description of the invention
Fig. 1 is the preparation route of MOFs- chitosan nano fiber composite membrane provided in an embodiment of the present invention.
Fig. 2 is the pictorial diagram of chitosan nano fiber prepared by the embodiment of the present invention 1.
Fig. 3 is the SEM figure of chitosan nano fiber prepared by the embodiment of the present invention 1.
Fig. 4 is the pictorial diagram of ZIF-8- chitosan nano fiber composite membrane prepared by the embodiment of the present invention 1.
Fig. 5 is the SEM figure of ZIF-8- chitosan nano fiber composite membrane prepared by the embodiment of the present invention 1.
Fig. 6 is the strength character of ZIF-8- chitosan nano fiber composite membrane prepared by the embodiment of the present invention 1.
Fig. 7 is the SEM figure that the embodiment of the present invention 2 prepares ZIF-67- chitosan nano fiber composite membrane.
Fig. 8 is the ZIF-67 of 2 preparation of present invention verifying and the SEM of chitosan nano fiber blend film schemes.
Specific embodiment
The feasibility of this method is further described below by way of specific implementation example, but is not intended that the invention be limited to
These examples.
Chitosan nano fiber of the present invention is to obtain specific surface area with higher by nanotechnology treatments by chitosan
With the chitosan nano fiber of porosity, the variation of this form can greatly improve the MOFs retention performance of chitosan.Benefit
Preparing chitosan nano fiber with method of electrostatic spinning has many advantages, such as that manufacturing device is simple, cost of spinning is cheap, technique is controllable, but
Obtained chitosan nano fiber intensity is lower, and stability is poor in water or other solvents；And again by by aldehyde bifunctional,
Acid anhydrides or epoxy resin etc. are crosslinked to get the product for the water resistance for arriving reticular structure, while improving fibre strength.
Embodiment 1
The preparation of ZIF-8- chitosan nano fiber composite membrane
1) chitosan and polyethylene glycol oxide the preparation of chitosan nano fiber: are respectively added slowly to conduct in glacial acetic acid
Total solution, wherein glacial acetic acid final concentration (mass concentration) is 3% in total solution, and chitosan accounts for the 1% of total solution quality, polyoxy
Change ethylene and account for the 0.5% of total solution quality, opens magnetic stirring apparatus, revolving speed 500r/min, solid is completely molten after stirring 30min
Solution；Solution after ultrasound 30min, is extracted solution with the syringe of 5mL and carries out electrostatic spinning under the intensity of 1500W after dissolution,
Using tinfoil as receiver board, spinning condition are as follows: positive pressure 2.0KV, negative pressure are -5.0KV, and injecting speed is 0.02mm/min,
Translational velocity is 100mm/min, and the revolving speed for receiving roller is 5r/min；After spinning, tinfoil is removed, is cut into 2cm × 2cm
Fritter, chitin fiber is removed into (Fig. 2, Fig. 3) from tinfoil；
2) it the preparation of ZIF-8: weighs 3.712g zinc nitrate hexahydrate and is placed in 5mL ethanol solution, while taking 2- methyl
Imidazoles 1.875g is dissolved in 5mL ethanol solution, after obtaining two kinds of solution mixing concussion 10s, is then reacted at room temperature
12h filters solution after reaction, with 12h is dried in vacuo after washes of absolute alcohol filter residue 5 times, can be obtained ZIF-8
Grain；
3) chitosan nano fiber and ZIF-8 the preparation of ZIF-8- chitosan nano fiber composite membrane: are added to methanol
In, wherein the dosage of ZIF-8 is the 5% of chitosan nano fiber, and the dosage of methanol is 50 times of chitosan nano fiber, body
It ties up under the stirring rate of 100r/min and reacts at room temperature 0.5h；Then it is added in system relative to chitin fiber quality 1%
Glutaraldehyde, 1h is crosslinked under the stirring rate of 100r/min, is filtered after reaction, is washed 3 times, can be obtained with dehydrated alcohol
To ZIF-8- chitosan nano fiber composite membrane, as shown in Figure 4, Figure 5.
Verifying 1
The strength character of ZIF-8- chitosan nano fiber composite membrane
The ZIF-8 prepared in above-described embodiment 1 and chitosan nano fiber is taken to be added in methanol, wherein the use of ZIF-8
Amount is the 5% of chitosan nano fiber, and the dosage of methanol is 50 times of chitosan nano fiber, in the stirring rate of 100r/min
Lower mixing 1h is washed 3 times with dehydrated alcohol, air-dries, ZIF-8- chitosan nano fiber blend film can be obtained.By ZIF-8- shell
ZIF-8- chitosan nano fiber composite membrane obtained in glycan nano-fibre blend film and embodiment 1 is surveyed using tensilon
The tensile strength of film is tried, as shown in Figure 6.It can be seen from the figure that the ZIF-8- chitosan nano fiber by crosslinking is compound
Film-strength reaches as high as 125MPa, cannot measure without the blend film of crosslinking since intensity is too low.Meanwhile ZIF-8- shell is poly-
The retention of ZIF-8 is up to 67.1% in sugared nano-fiber composite film.Therefore, which can greatly improve ZIF-8-
The compound film strength of chitosan nano fiber.
Embodiment 2
The preparation of ZIF-67- chitosan nano fiber composite membrane
1) chitosan and polyethylene glycol oxide the preparation of chitosan nano fiber: are respectively added slowly to conduct in glacial acetic acid
Total solution, wherein glacial acetic acid final concentration (mass concentration) is 5% in total solution, and chitosan accounts for the 3% of total solution quality, polyoxy
Change ethylene and account for the 1% of total solution quality, opens magnetic stirring apparatus, revolving speed 500r/min, solid is completely molten after stirring 30min
Solution；Solution after ultrasound 30min, is extracted solution with the syringe of 5mL and carries out electrostatic spinning under the intensity of 1500W after dissolution,
Using tinfoil as receiver board, spinning condition are as follows: positive pressure 13KV, negative pressure are -10.0KV, and injecting speed is 0.02mm/min,
Translational velocity is 500mm/min, and the revolving speed for receiving roller is 30r/min；After spinning, tinfoil is removed, be cut into 2cm ×
The fritter of 2cm removes chitin fiber from tinfoil；
2) preparation of ZIF-67 particle: weighing CoCL2 6H2O 2.5g and 1g 2-methylimidazole is added in 5mL methanol,
It is filtered after reacting 12h at room temperature, ZIF-67 particle can be obtained after cleaning filter residue 5 times with methanol；
3) chitosan nano fiber and ZIF-67 the preparation of ZIF-67- chitosan nano fiber composite membrane: are added to nothing
In water-ethanol, wherein the dosage of ZIF-67 is the 20% of chitosan nano fiber, and dehydrated alcohol dosage is chitosan nano fiber
500 times, system reacts at room temperature 0.5h under the stirring rate of 100r/min；Then it is added in system relative to chitosan fibre
The glyoxal for tieing up quality 10%, 3h is crosslinked under the stirring rate of 500r/min, is filtered after reaction, is washed with dehydrated alcohol
3 times, ZIF-67- chitosan nano fiber composite membrane (as shown in Figure 7) can be obtained.
Verifying 2
The solvent resistance of ZIF-67- chitosan nano fiber composite membrane
The ZIF-67 prepared in above-described embodiment 2 and chitosan nano fiber is taken to be added in methanol, wherein ZIF-67's
Dosage is the 20% of chitosan nano fiber, and the dosage of methanol is 500 times of chitosan nano fiber, in the stirring of 500r/min
3h is mixed under rate, is washed 3 times with dehydrated alcohol, ZIF-67- chitosan nano fiber blend film (referring to Fig. 8) can be obtained,
By comparison diagram 7 and Fig. 8, it is apparent that the ZIF-67- chitosan nano fiber blend film of crosslinking agent, ZIF-67 is not used
It is simply deposited in fiber surface, and dispersed poor (Fig. 8), and the ZIF-67- chitosan nano fiber composite membrane after being crosslinked
Middle ZIF-67 is evenly dispersed, does not occur the phenomenon that reunion (Fig. 7).Meanwhile it can be seen from Table 1 that, the ZIF-67- shell after crosslinking
Glycan nano-fiber composite film is in five kinds of different solvents (water, DMAC N,N' dimethyl acetamide, tetrahydrofuran, ethyl alcohol and acetone)
Dipping is after 48 hours, and mass loss is only 3% or so, and the quality of uncrosslinked ZIF-67- chitosan nano fiber blend film
Loss is all larger than 50%, and is completely dispersed after impregnating in water, cannot form.This explanation, ZIF-67 and chitosan after crosslinking
Nanofiber and chitosan nano fiber internal combustion are more close, and water-fast and solvent resistance greatly improves.
Table 1 is the solvent resistance of the ZIF-67- chitosan nano fiber composite membrane prepared.
| Mass loss (%) after solvent soaking 48h | Water | DMAC N,N' dimethyl acetamide | Tetrahydrofuran | Ethyl alcohol | Acetone |
| ZIF-67- chitosan nano fiber blend film | 100 | 59.17 | 63.60 | 61.43 | 64.05 |
| ZIF-67- chitosan nano fiber composite membrane | 3.13 | 2.72 | 2.25 | 3.57 | 3.80 |
Embodiment 3
The preparation of MIL-101 (Cr)-chitosan nano fiber composite membrane
1) chitosan and polyethylene glycol oxide the preparation of chitosan nano fiber: are respectively added slowly to conduct in glacial acetic acid
Total solution, wherein glacial acetic acid final concentration (mass concentration) 4% in total solution, chitosan accounts for the 2% of total solution quality, polyoxygenated
Ethylene accounts for the 0.1% of total solution quality, opens magnetic stirring apparatus, revolving speed 500r/min, solid is completely molten after stirring 30min
Solution；Solution after ultrasound 30min, is extracted solution with the syringe of 5mL and carries out electrostatic spinning under the intensity of 1500W after dissolution,
Using tinfoil as receiver board, spinning condition are as follows: positive pressure 5.0KV, negative pressure are -6.0KV, and injecting speed is 0.05mm/min,
Translational velocity is 300mm/min, and the revolving speed for receiving roller is 20r/min；After spinning, tinfoil is removed, be cut into 2cm ×
The fritter of 2cm removes chitin fiber from tinfoil；
2) it the preparation of MIL-101 (Cr) particle: weighs Chromium nitrate (Cr(NO3)3),nonahydrate 0.15g and terephthalic acid (TPA) 0.5g and is added to
In 5mL methanol, after two kinds of solution concussion 10s will be obtained, 12h is then reacted at room temperature, solution after reaction is filtered,
It is dried in vacuo 12h after cleaning filter residue 5 times with methanol, MIL-101 (Cr) particle can be obtained；
3) MIL-101 (Cr)-chitosan nano fiber composite membrane preparation: by chitosan nano fiber and MIL-101
(Cr) it is added in dehydrated alcohol, wherein the dosage of MIL-101 (Cr) is the 10% of chitosan nano fiber, and dehydrated alcohol is used
Amount is 300 times of chitosan nano fiber, and system reacts at room temperature 0.5h under the stirring rate of 100r/min；Then in system
The epoxychloropropane relative to chitin fiber quality 5% is added, 2h is crosslinked under the stirring rate of 800r/min, reaction terminates
After filter, washed 3 times with dehydrated alcohol, MIL-101 (Cr)-chitosan nano fiber composite membrane can be obtained.
Verifying 3
The performance test of MIL-101 (Cr)-chitosan nano fiber composite membrane
The MIL-101 (Cr) prepared in above-described embodiment 3 and chitosan nano fiber is taken to be added in dehydrated alcohol,
In, the dosage of MIL-101 (Cr) is the 10% of chitosan nano fiber, and the dosage of dehydrated alcohol is chitosan nano fiber
300 times, 2h is mixed under the stirring rate of 800r/min, is washed 3 times with dehydrated alcohol, air-dries, MIL-101 can be obtained
(Cr)-chitosan nano fiber blend film.It will be obtained in MIL-101 (Cr)-chitosan nano fiber blend film and example 3
MIL-101 (Cr)-chitosan nano fiber composite membrane tests the tensile strength of film using tensilon.By crosslinking
MIL-101 (Cr)-compound film-strength of chitosan nano fiber reaches as high as 92.4MPa, without the blend film of crosslinking due to strong
It spends too low and cannot measure.In addition, by test, MIL-101 (Cr) in MIL-101 (Cr)-chitosan nano fiber composite membrane
Retention is 48.3%, and MIL-101 (Cr)-chitosan nano fiber blend film MIL-101 (Cr) retention is only
6.1%.This illustrates that crosslinked action not only significantly improves MIL-101 (Cr)-compound film strength of chitosan nano fiber, but also
Improve the retention of MIL-101 (Cr).
Embodiment 4
The preparation of HKUST-1- chitosan nano fiber composite membrane
1) chitosan and polyethylene glycol oxide the preparation of chitosan nano fiber: are respectively added slowly to conduct in glacial acetic acid
Total solution, wherein glacial acetic acid final concentration (mass concentration) 3.5% in total solution, chitosan accounts for the 2% of total solution quality, polyoxy
Change ethylene and account for the 0.2% of total solution quality, opens magnetic stirring apparatus, revolving speed 500r/min, solid is completely molten after stirring 30min
Solution；Solution after ultrasound 30min, is extracted solution with the syringe of 5mL and carries out electrostatic spinning under the intensity of 1500W after dissolution,
Using tinfoil as receiver board, spinning condition are as follows: positive pressure 10.0KV, negative pressure are -9.0KV, and injecting speed is 0.05mm/min,
Translational velocity is 200mm/min, and the revolving speed for receiving roller is 9r/min；After spinning, tinfoil is removed, is cut into 2cm × 2cm
Fritter, chitin fiber is removed from tinfoil；
2) preparation of HKUST-1 particle: weighing Salicylaldoxime 0.25g and trimesic acid 0.5g is placed in 5mL alcoholic solution,
After obtaining two kinds of solution concussion 10s, 12h is then reacted at room temperature, solution after reaction is filtered, cleans filter with alcohol
It is dried in vacuo 12h after slag 5 times, HKUST-1 particle can be obtained；
3) preparation of HKUST-1- chitosan nano fiber composite membrane: chitosan nano fiber and HKUST-1 are added to
In methanol, wherein the dosage of HKUST-1 is the 15% of chitosan nano fiber, and methanol usage is the 150 of chitosan nano fiber
Times, system reacts at room temperature 0.5h under the stirring rate of 100r/min；Then it is added in system relative to chitin fiber matter
The glutaraldehyde of amount 4%, 1.5h is crosslinked under the stirring rate of 300r/min, is filtered after reaction, washs 3 times with methanol, i.e.,
HKUST-1- chitosan nano fiber composite membrane can be obtained.
Verifying 4
The retention test of HKUST-1 in HKUST-1- chitosan nano fiber composite membrane
HKUST-1- chitosan nano fiber blend film is prepared for using with 3 identical methods of verifying.By test, it is blended
The retention of HKUST-1 is 2.3% in film, and the composite membrane HKUST-1 retention after being crosslinked in example 4 is up to 41.2%.
Embodiment 5
UiO-66-NH2The preparation of chitosan nano fiber composite membrane
1) chitosan and polyethylene glycol oxide the preparation of chitosan nano fiber composite membrane: are respectively added slowly to glacial acetic acid
It is middle to be used as total solution, wherein glacial acetic acid final concentration (mass concentration) is 5% in total solution, and chitosan accounts for total solution quality
3%, polyethylene glycol oxide accounts for the 0.8% of total solution quality, opens magnetic stirring apparatus, and revolving speed 500r/min consolidates after stirring 30min
Body is completely dissolved；Solution after ultrasound 30min, is carried out quiet under the intensity of 1500W with the syringe of 5mL extraction solution after dissolution
Electrospun, using tinfoil as receiver board, spinning condition are as follows: positive pressure 7.0KV, negative pressure are -6.0KV, and injecting speed is
0.1mm/min, translational velocity 400mm/min, the revolving speed for receiving roller is 30r/min；After spinning, tinfoil is removed,
It is cut into the fritter of 2cm × 2cm, chitin fiber is removed from tinfoil；
2)UiO-66-NH2The preparation of particle: the conical flask that zirconium chloride (93.2mg, 0.4mmol) is placed in 25 milliliters is weighed
In, it is added n,N-Dimethylformamide (16mL), acetic acid (1200mg, 20mmol) then is added, sonic oscillation 30min makes it
It is completely dissolved, organic ligand 2- amino terephthalic acid (TPA) (72.5mg, 0.4mmol) then is added, then sonic oscillation 30min, dress
Into the high temperature and high pressure kettle of 20mL, 120 DEG C of constant temperature are cooled to 20 DEG C for 24 hours, by 10h, obtain faint yellow nano crystals
(120mg), after being cleaned with chloroform, centrifugation, UiO-66-NH is can be obtained in dry 3h at 100 DEG C2Particle；
3)UiO-66-NH2The preparation of chitosan nano fiber composite membrane: by chitosan nano fiber and UiO-66-NH2Add
Enter into methanol, wherein UiO-66-NH2Dosage be the 9% of chitosan nano fiber, methanol usage is that chitosan nano is fine
450 times of dimension, system reacts at room temperature 0.5h under the stirring rate of 100r/min；Then it is added in system relative to chitosan
The epoxychloropropane of fiber quality 8% is crosslinked 2.5h under the stirring rate of 450r/min, filters after reaction, uses methanol
Washing 3 times, can be obtained UiO-66-NH2Chitosan nano fiber composite membrane.
Verifying 5
UiO-66-NH2The strength character of chitosan nano fiber composite membrane
UiO-66-NH is prepared for using with 3 identical methods of verifying2Chitosan nano fiber blend film.It is surveyed by intensity
Examination, the tensile strength of the composite membrane prepared in example 5 are 41.4MPa, and it is lower to be blended film-strength, can not measure.Therefore, pass through
The mechanical performance of crosslinked composite membrane is greatly improved.
Embodiment 6
The preparation of MOFs-74 (Ni)-chitosan nano fiber composite membrane
1) chitosan and polyethylene glycol oxide the preparation of chitosan nano fiber: are respectively added slowly to conduct in glacial acetic acid
Total solution, wherein glacial acetic acid final concentration (mass concentration) is 10% in total solution, and chitosan accounts for the 5% of total solution quality, polyoxy
Change ethylene and account for the 10% of total solution quality, opens magnetic stirring apparatus, revolving speed 500r/min, solid is completely molten after stirring 30min
Solution；Solution after ultrasound 30min, is extracted solution with the syringe of 5mL and carries out electrostatic spinning under the intensity of 1500W after dissolution,
Using tinfoil as receiver board, spinning condition are as follows: positive pressure 13.0KV, negative pressure are -10.0KV, and injecting speed is 0.15mm/
Min, translational velocity 500mm/min, the revolving speed for receiving roller is 30r/min；After spinning, tinfoil is removed, is cut into 2cm
The fritter of × 2cm removes chitin fiber from tinfoil；
2) preparation of MOFs-74 (Ni) is by 0.36g NiCl2·6H2It is molten that O and 0.15g terephthalic acid (TPA) is added to 35mLDMF
In agent, the triethylamine of 0.5mL is added to being completely dissolved in ultrasonic 20min, which is quickly transferred to ultrasonator
In, ultrasonic 6h；Finally, reactant is centrifuged, washed 5 times with DMF reagent, being dried in vacuum overnight at 80 DEG C can be obtained MOFs-
74(Ni)；
3) MOFs-74 (Ni)-chitosan nano fiber composite membrane preparation: by chitosan nano fiber and MOFs-74
(Ni) it is added in dehydrated alcohol, wherein the dosage of MOFs-74 (Ni) is the 30% of chitosan nano fiber, and dehydrated alcohol is used
Amount is 500 times of chitosan nano fiber, and system reacts at room temperature 0.5h under the stirring rate of 100r/min；Then in system
The silane coupling agent relative to chitin fiber quality 20% is added, 5h, reaction knot are crosslinked under the stirring rate of 1000r/min
It filters after beam, is washed 3 times with dehydrated alcohol, MOFs-74 (Ni)-chitosan nano fiber composite membrane can be obtained.
Verifying 6
The test of MOFs-74 (Ni)-chitosan nano fiber composite membrane retention
MOFs-74 (Ni)-chitosan nano fiber blend film is prepared for using with 3 identical methods of verifying.By keeping
MOFs-74 (Ni) retention of the test of rate, blend film is only 3%, and MOFs-74 (Ni) retention can in composite membrane after being crosslinked
Up to 12%.Therefore, MOFs-74 can be improved by MOFs-74 prepared by the present invention (Ni)-chitosan nano fiber composite membrane
(Ni) retention.
In summary example, the present invention by cross-linking method by chitosan nano fiber in conjunction with MOFs, be successfully prepared
MOFs- chitosan nano fiber Composite Films Composite films.The example is demonstrated by the resulting composite membrane of the preparation method
MOFs's is uniformly dispersed, orderly aligned, does not occur the phenomenon that reunion, and MOFs retention is higher.Meanwhile MOFs in composite membrane
It is tightly combined with chitosan nano fiber, and significantly improves the intensity after chitosan nano fiber is blended with MOFs, water-fast
And solvent resistance.In addition, being somebody's turn to do, preparation method is simple, and preparation condition is mild, is suitble to large-scale production, has wide application
Prospect.
Claims (9)
1. a kind of preparation method of MOFs- chitosan nano fiber composite membrane, it is characterized in that: being prepared by method of electrostatic spinning
Chitosan nano fiber, it is then, compound under crosslinking action after the MOFs material of synthesis is blended with chitosan nano fiber,
Obtain MOFs- chitosan nano fiber composite membrane.
2. the preparation method of MOFs- chitosan nano fiber composite membrane according to claim 1, it is characterized in that: the MOFs
Material is dissolved in organic solvent with chitosan nano fiber dispersion is blended after crosslinking agent is added, filtering after reaction, organic solvent washes
It washs, obtains MOFs- chitosan nano fiber composite membrane；The organic solvent be methanol or dehydrated alcohol, wherein organic solvent with
Chitosan nano fiber volume mass ratio is 50-500:1.
3. the preparation method of MOFs- chitosan nano fiber composite membrane according to claim 1, it is characterized in that: the crosslinking
Agent is that glutaraldehyde, glyoxal, formaldehyde, silane coupling agent, inorganic crosslinking agent, amino resins, phenolic resin, epoxy resin are therein
One or more, dosage are the 0.1%-20% of chitosan nano fiber quality.
4. the preparation method of MOFs- chitosan nano fiber composite membrane according to claim 1, it is characterized in that: the crosslinking
Technique is to stir 0.5h-5h under 50r/min-1000r/min rate.
5. the preparation method of MOFs- chitosan nano fiber composite membrane according to claim 1, it is characterized in that: the shell is poly-
Sugared nanofiber be by chitosan be raw material by electrostatic spinning in a manner of the diameter that obtains be less than the fiber of 200nm.
6. the preparation method of MOFs- chitosan nano fiber composite membrane as described in claim 5, it is characterized in that: the shell is poly-
Sugared nanofiber be by chitosan be raw material by wet electrostatic spinning in a manner of prepare, by chitosan and polyethylene glycol oxide
It is respectively added slowly in concentrated acid solution, water is added after mixing and obtains uniformly sticky chitosan solution to be spun, then at ultrasound
Electrostatic spinning is carried out after reason, and chitin fiber is obtained after removing；Wherein, final concentration of 1%- sour in chitosan solution to be spun
10%, chitosan accounts for the 0.5%-5% of acid solution quality, and polyethylene glycol oxide accounts for the 0.1%-10% of acid solution quality.
7. the preparation method of MOFs- chitosan nano fiber composite membrane according to claim 6, it is characterized in that: solution is surpassed
After sound, solution is extracted with syringe and carries out electrostatic spinning, using tinfoil as receiver board, spinning condition are as follows: positive pressure 2.0KV-
13.0KV, negative pressure are -5.0KV--10.0KV, and injecting speed is 0.02mm/min-0.15mm/min, translational velocity 100mm/
Min-500mm/min, the revolving speed for receiving roller is 5r/min-30r/min.
8. the preparation method of MOFs- chitosan nano fiber composite membrane according to claim 1, it is characterized in that: the MOFs
Material is made of metal salt and ligand, wherein metal salt refer to using major element, transition elements or lanthanide series as metal sun from
One or more of the water soluble salt of son；Dosage is the 1%-30% of chitosan nano fiber quality；
Ligand refers to one or more of oxygen-containing or nitrogen organic anionic ligands containing carboxyl, or with nitrogen-containing heterocycle organic neutral
Ligand is used in conjunction with, and ligand additional amount is the 1%-30% of chitosan nano fiber quality.
9. the preparation method of MOFs- chitosan nano fiber composite membrane according to claim 8, it is characterized in that: the metal
Salt is zinc nitrate, cobalt chloride, copper acetate, chromic nitrate, zirconium chloride or nickel chloride, and dosage is chitosan nano fiber quality
5%-20%；
Ligand is 2-methylimidazole, trimesic acid, terephthalic acid (TPA), 2- amino terephthalic acid (TPA), terephthalic acid (TPA), and dosage is shell
The 5%-20% of glycan nanofiber quality.
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