CN110368823A - A kind of preparation method of metal organic frame-polyimide composite fiber membrane material - Google Patents
A kind of preparation method of metal organic frame-polyimide composite fiber membrane material Download PDFInfo
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- CN110368823A CN110368823A CN201910207227.6A CN201910207227A CN110368823A CN 110368823 A CN110368823 A CN 110368823A CN 201910207227 A CN201910207227 A CN 201910207227A CN 110368823 A CN110368823 A CN 110368823A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
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- 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
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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
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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
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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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
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Abstract
The present invention relates to a kind of preparations of metal organic frame-polyimide composite fiber membrane material, first in methanol system, ZIF-8 is prepared for by the quick method of room temperature, imidization is carried out again, and soluble polyimide 6FDA-BDAF is made, ZIF/PI composite cellulosic membrane is prepared for using simple electrostatic spinning technique later, obtained membrane material thermal stability with higher and mechanical strength, and the interconnecting network structure to be formed by nanofiber random distribution, its diameter range is distributed in 200-300 nanometers, ZIF-8 is well dispersed in PI matrix, reunite without obvious, and with the addition of ZIF-8, the fiber surface of otherwise smooth becomes coarse, the frequency that superfine fibre occurs simultaneously increases, so that the specific surface area of material increases, with stronger capture PM 2.5 abilities, it is important that preparation method is easy, and reaction condition is mildly easily-controllable, is conducive to large-scale production, and good performance and easy preparation method make it have broad application prospects in high temperature air filtration art.
Description
Technical field
The present invention relates to functional material preparation technical fields, and in particular to a kind of metal organic frame-polyimides is compound
The preparation method of fiber film material.
Background technique
Polyimides (PI) is that a kind of organic polymer that main chain contains imide ring and comprehensive performance are optimal organic
One of high molecular material, has many advantages, such as high insulating property, and high mechanical strength, high thermal stability and wear-resistant are widely used in
The fields such as Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, seperation film, laser.In addition, also there is polyimides high dipole moment (to reach
It is more much higher than the common dipole moment for actively capturing polymer to 6.2D), therefore it is with extremely strong PM2.5 capture ability, polyamides
The excellent physical and chemical performance of imines has also pushed it in the application of field of air filtration.
Traditional air filting material improves filter efficiency often through increasing bulk density or reducing fiber aperture,
However the operation will increase air flow resistance, bring discomfort to user；And with the development of science and technology, people are to air mistake
Filter material material is put forward higher requirements, and other than PM filter efficiency and pressure drag, that thermal stability, mechanical performance etc. also become measurement is new
The important indicator of type filtering material.Polyimide fiber film has excellent thermal stability and mechanical performance, carries out function to it
Change and be modified, under the premise of not damaging original performance, further increase its filter capacity to PM2.5, polyamides Asia can be widened
Amine filtering material also provides a kind of feasible approach in the application prospect of field of air filtration for PM contamination control.
Metal organic framework (Metal-Organic Frameworks, MOF) is by metal ion and organic ligand structure
At frame structure.Some MOF materials not only have the function of that large specific surface area, structure and hole diversity, adjustability etc. are special
Point also shows high PM2.5 capture ability.In recent years, MOF material is become into novel air filtering in conjunction with polymer
The research hotspot of material, " american chemical magazine " (J.Am.Chem.Soc.2016,138,5785-5788.) report one kind
MOF/ polyacrylonitrile composite fiber membrane material can be realized simultaneously sky by loading MOF material on polyacrylonitrile nanofiber
The filtering of PM particle and toxic gas in gas, however since the interaction of MOF and polymeric matrix is poor, so that the composite membrane
The mechanical performance and stability of material are poor；" chemical engineering magazine " (Chemical Engineering Journal 2018,
338,82-91.) a kind of ZIF-8/ PLA Composite Fiber membrane material is reported, since polylactic acid and ZIF-8 have good boundary
Face interaction, so that the PM filter efficiency of composite membrane is further improved under the premise of not damaging substrate performance, but it is poly-
Lactic acid itself heat resistance and mechanical performance are poor, can not also use under harsh working environment.
In conjunction with above-mentioned, in conjunction with the advantages of polyimide material and metal organic frame, it is poly- to provide a kind of metal organic frame-
Acid imide composite fiber membrane material is the hot spot studied in the prior art, but in the prior art about polyimides and metal
The compound of organic frame mostly uses in-situ compositing, so that the two binding ability difference is influenced mechanical performance, and preparation process is multiple
It is miscellaneous to be difficult to operate, therefore a kind of easier technique how is provided to prepare metal organic frame-polyimide composite fiber membrane material
Material, making it not only has the filter capacity of good PM pollutant, but also have low pressure drag and higher heat resistance and
More excellent mechanical performance excellent properties are those skilled in the art's urgent problems to be solved.
Summary of the invention
In view of this, the present invention provides a kind of metal organic frame-polyimide composite fiber membrane material preparation sides
Method carries out electrospinning to metal organic frame and polyimides mixing material using electrostatic spinning technique, makes to have between the two more
Good binding ability, to have more excellent mechanical performance, and preparation process is easier.
To achieve the goals above, the present invention specifically uses following technological means:
A kind of preparation of metal organic frame-polyimide composite fiber membrane material, which is characterized in that including following step
It is rapid:
Step 1: the preparation of metal organic frame ZIF-8
A certain amount of methylimidazole and zinc nitrate are dissolved in methanol respectively, stood for 24 hours after later mixing two solution,
It is centrifugated after being cleaned with methanol, is placed in 120 DEG C of oven drying 12h to get ZIF-8；
Step 2: the preparation of soluble polyimide 6FDA-BDAF
(2.1) hexafluoropropane is dissolved in n,N-dimethylacetamide under the conditions of nitrogen and ice-water bath, to hexafluoropropane
Hexafluorodianhydride (6FDA) is added after being completely dissolved into mixed liquor, obtains to contain solid mixed solution later containing solid mixed solution and persistently stirring
1h；
(2.2) solid mixed solution will be contained and remove ice-water bath, acid anhydrides and pyridine is added after persistently stirring 20h at room temperature, continues
Viscosity solution is obtained after stirring 20h；
(2.3) viscosity solution is poured into excessive dehydrated alcohol, obtains filament resin, done at 80 DEG C after collecting filament resin
It is dry for 24 hours to get soluble polyimide 6FDA-BDAF；
Step 3: metal organic frame-polyimide composite fiber membrane material preparation
(3.1) metal organic frame ZIF-8 made from the step 1 is dissolved in n,N-dimethylacetamide, ultrasound point
Soluble polyimide 6FDA-BDAF made from the step 2 is added after dissipating 6h, until 1-3h is stirred at room temperature after being completely dissolved in it,
Obtain mixed liquor；
(3.2) mixed liquor is moved into electrostatic spinning apparatus, aluminium foil is collector, is arranged after electrospinning parameters through 1-2h electricity
It spins, takes electrospinning film off later, as metal organic frame-polyimide composite fiber membrane material.
Preferably, the molar ratio of the methylimidazole in the step 1 and zinc nitrate is (2-8): 1.
The beneficial effect of above-mentioned optimal technical scheme is: changing the proportion of methylimidazole and zinc nitrate, thus it is possible to vary
The partial size of ZIF-8, but ZIF-8 partial size, which crosses conference, makes the formation for influencing electrospinning fibre, partial size is too small, and serious group can occur
Poly- phenomenon limits the ZIF-8 of reasonable proportion preparation in the present invention, makes it have suitable particle size, both the group of being not susceptible to
It is poly-, and will not influence fiber filamentation process, prepared PI-ZIF composite fibre has uniform diameter and excellent performance.
Preferably, the centrifugal rotational speed 10000rpm in the step 1, centrifugation time 10min, and cleaning-centrifugal process weight
Again more than twice.
Preferably, the molar ratio of the hexafluoropropane in the step (2.1), n,N-dimethylacetamide and hexafluorodianhydride (6FDA)
It is 1: 63: 1.
The beneficial effect of above-mentioned optimal technical scheme is: both hexafluoropropane and hexafluorodianhydride (6FDA) molar ratio are 1: 1, and the two is handed over
For chaining, the degree of polymerization is high, and product property is excellent, and when the two molar ratio is not 1: 1, the degree of polymerization is low, and that there are residual monomers is miscellaneous
Matter, product property are poor.
Preferably, the acid anhydrides of ratio meter by weight, the addition in the step (2.2) is the 7.9wt% containing solid solution, pyrrole
Pyridine is the 6.2wt% containing solid solution.
The beneficial effect of above-mentioned optimal technical scheme is: the additional amount of acid anhydrides and pyridine is very few to will lead to product imine journey
It spends low, although additional amount is excessively high to have an impact product, will cause the waste of reagent, the ratio that the present invention limits
Ensure that the imidization degree of prepared soluble polyimide is high, has excellent performance, and raw material can be maximally utilized, avoid wave
Take.
Preferably, soluble polyimide 6FDA-BDAF, the metal organic frame ZIF- being added in the step (3.1)
8, the mass ratio of n,N-dimethylacetamide is 0.4: (0.01-0.04): 2.
Preferably, in the step (3.2) coaxial electrically spun technological parameter are as follows: receiver is with filator injection port distance
15cm, spinning voltage 15kV, ambient humidity < 40%, 20-30 DEG C of temperature.
The beneficial effect of above-mentioned optimal technical scheme is: the selection of spinning voltage and spinning distance has very big shadow to film forming
It rings, with the raising of spinning voltage and the increase of spinning distance, overtension or hypertelorism can all influence receiver to spinning
Reception, influence film-formation result, and liquid difficulty is volatilized in the too low spinning solution of humidity excessive temperature, the excessively high evaporation rate of temperature is fast
It is difficult to be received by the receiver, the integrality of film forming is impacted, in the above-mentioned voltage of the invention limited and receiver distance
Under the conditions of humidity temperature, it is ensured that composite material film forming is complete uniform, makes it have good performance.
In conclusion compared with prior art, the present invention has following technical effect that
That present invention incorporates metal framework structure ZIF-8Zeta current potentials is high, thermal stability is good and polyimide material machine
The advantages that tool intensity is high, thermal stability is good and good PM2.5 capture ability, prepared ZIF/PI film both remains polyamides
The advantage of imine fiber film high-mechanical property and thermal stability, while further improving filtering of the composite cellulosic membrane to PM2.5
Efficiency, it is important that technical solution of the present invention is easy to operate, and preparation condition is mild, is easy to be mass produced, good performance
And easy preparation method makes it have broad application prospects in high temperature air filtration art.
Figure of description
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 attached drawing is the XRD diffraction spectrogram of ZIF-8 produced by the present invention；
Fig. 2 attached drawing is the scanning electron microscope (SEM) photograph of ZIF-8 produced by the present invention；
Fig. 3 attached drawing is the infrared spectroscopy of soluble polyimide 6FDA-BDAF produced by the present invention；
Fig. 4 attached drawing is that the SEM/EDS of PI-ZIF-10 composite fibre produced by the present invention schemes；
Fig. 5 attached drawing is the thermogravimetric curve figure of PI-ZIF composite fibre produced by the present invention；
Fig. 6 attached drawing is the strainability test chart of PI-ZIF composite fibre produced by the present invention；
Fig. 7 attached drawing is the strainability test chart after PI-ZIF composite fibre produced by the present invention heat treatment；
Fig. 8 attached drawing is the stress-strain curve of PI-ZIF composite fibre produced by the present invention；
Fig. 9 attached drawing is wind speed-falloff curve figure of PI-ZIF composite fibre produced by the present invention；
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
The preparation of metal organic frame ZIF-8
1.621g (20mol) methylimidazole and 1.291g (4.3mol) zinc nitrate are dissolved in respectively in 50ml methanol, it
Afterwards will two solution mix after stand for 24 hours, after being cleaned with methanol, 10000rpm be centrifuged 10min, repeated washing-centrifugation twice, later
120 DEG C of oven drying 12h are placed in get ZIF-8.
ZIF-8 obtained above is characterized, by attached drawing 1 it is found that the present invention prepare the diffraction spectra of product with it is known
Standard diffraction spectrum is completely the same, shows that the product is ZIF-8；By Fig. 2 scanning electron microscope (SEM) photograph it is found that ZIF-8 produced by the present invention
The equidistant nanoparticle that particle has sharp edges, particle diameter distribution narrow carries out statistical estimation, obtained result to 100 particles
It is average diameter is 95 nanometers, and pattern is good；
To ZIF-8 produced by the present invention after the heat treatment of 300 DEG C of 1h, original crystalline structure, table can be still kept
It is bright its with excellent thermal stability.
Embodiment 2
The preparation of soluble polyimide 6FDA-BDAF
(2.1) 5.185g (10mol) hexafluoropropane is dissolved in 54.6g (630mol) N, N- under the conditions of nitrogen and ice-water bath
In dimethyl acetamide, 4.442g (10mol) hexafluorodianhydride (6FDA) is added into mixed liquor after hexafluoropropane is completely dissolved, is contained
Admittedly measuring the mixed solution of 15wt%, solid mixed solution will be contained later and persistently stir 1h；
(2.2) solid mixed solution will be contained and remove ice-water bath, 5.1g acid anhydrides and 4.0g pyrrole is added after persistently stirring 20h at room temperature
Pyridine continues to obtain viscosity solution after stirring 20h；
(2.3) viscosity solution is poured into excessive dehydrated alcohol, obtains filament resin, done at 80 DEG C after collecting filament resin
It is dry for 24 hours to get soluble polyimide 6FDA-BDAF.
Carrying out infrared spectrum characterization to soluble polyimide obtained above as a result as shown in Fig. 3 can by attached drawing 3
Know, in 1786cm-1It is nearby the asymmetric stretching vibration of C=O key, 1727cm-1It is nearby the symmetrical stretching vibration of C=O key,
723cm-1The deformation of imide ring, 1375cm are nearby corresponded to-1It is nearby the stretching vibration of C-N key, in addition, in 3363cm-1(N-H
Stretching vibration) and 1650cm-1The absorption peak of (amide C=O stretching vibration) disappears, and shows that 6FDA-BDAF realizes complete Asia
Aminating process.
Embodiment 3
The preparation of metal organic frame-polyimide composite fiber membrane material
(3.1) metal organic frame ZIF-8 0.01g made from embodiment 1 is dissolved in 2gN, in N- dimethyl acetamide,
Soluble polyimide 6FDA-BDAF 0.4g made from embodiment 2 is added after ultrasonic disperse 6h, until it is completely dissolved rear room temperature
1-3h is stirred, mixed liquor is obtained；
(3.2) mixed liquor is moved into electrostatic spinning apparatus, aluminium foil is collector, and receiver is with filator injection port distance
15cm, spinning voltage 15kV, ambient humidity < 40%, through 1-2h electrospinning, take electrospinning film off later to get gold by 20-30 DEG C of temperature
Belong to organic frame-polyimide composite fiber membrane material.
Wherein, the load capacity of ZIF-8 is the 2.5wt% of 6FDA-BDAF, is denoted as PI-ZIF-2.5.
Embodiment 4
The preparation of metal organic frame-polyimide composite fiber membrane material
(3.1) metal organic frame ZIF-8 0.02g made from embodiment 1 is dissolved in 2gN, in N- dimethyl acetamide,
Soluble polyimide 6FDA-BDAF 0.4g made from embodiment 2 is added after ultrasonic disperse 6h, until it is completely dissolved rear room temperature
1-3h is stirred, mixed liquor is obtained；
(3.2) mixed liquor is moved into electrostatic spinning apparatus, aluminium foil is collector, and receiver is with filator injection port distance
15cm, spinning voltage 15kV, ambient humidity < 40%, 20-30 DEG C of temperature, through 1-2h electrospinning, take off later electrospinning film to get
The load capacity of ZIF-8 is metal organic frame-polyimide composite fiber membrane material of 5wt%.
Wherein, the load capacity of ZIF-8 is the 5wt% of 6FDA-BDAF, is denoted as PI-ZIF-5.
Embodiment 5
The preparation of metal organic frame-polyimide composite fiber membrane material
(3.1) metal organic frame ZIF-8 0.03g made from embodiment 1 is dissolved in 2gN, in N- dimethyl acetamide,
Soluble polyimide 6FDA-BDAF 0.4g made from embodiment 2 is added after ultrasonic disperse 6h, until it is completely dissolved rear room temperature
1-3h is stirred, mixed liquor is obtained；
(3.2) mixed liquor is moved into electrostatic spinning apparatus, aluminium foil is collector, and receiver is with filator injection port distance
15cm, spinning voltage 15kV, ambient humidity < 40%, 20-30 DEG C of temperature, through 1-2h electrospinning, take off later electrospinning film to get
The load capacity of ZIF-8 is metal organic frame-polyimide composite fiber membrane material of 7.5wt%.
Wherein, the load capacity of ZIF-8 is the 7.5wt% of 6FDA-BDAF, is denoted as PI-ZIF-7.5.
Embodiment 6
The preparation of metal organic frame-polyimide composite fiber membrane material
(3.1) metal organic frame ZIF-8 0.04g made from embodiment 1 is dissolved in 2gN, in N- dimethyl acetamide,
Soluble polyimide 6FDA-BDAF 0.4g made from embodiment 2 is added after ultrasonic disperse 6h, until it is completely dissolved rear room temperature
1-3h is stirred, mixed liquor is obtained；
(3.2) mixed liquor is moved into electrostatic spinning apparatus, aluminium foil is collector, and receiver is with filator injection port distance
15cm, spinning voltage 15kV, ambient humidity < 40%, 20-30 DEG C of temperature, through 1-2h electrospinning, take off later electrospinning film to get
The load capacity of ZIF-8 is metal organic frame-polyimide composite fiber membrane material of 10wt%.
Wherein, the load capacity of ZIF-8 is the 10wt% of 6FDA-BDAF, is denoted as PI-ZIF-10.
Embodiment 7
Functional test is carried out to metal organic frame made from above-described embodiment-polyimide composite fiber membrane material,
Test process and result are as follows:
1. heat stability testing
The thermal stability of nano fibrous membrane is determined by weight change of the sample under the continuous elevation process of temperature, in this test
Weigh 3mg metal organic frame-polyimide composite fiber membrane material, in air atmosphere with the heating rate of 10 DEG C/min from
Room temperature is heated to 800 DEG C, and the thermogravimetric curve of sample is drawn out according to quality of the sample in different temperatures, such as 5 institute of attached drawing
Show.
Attached drawing 5 shows that the decomposition of PI (6FDA-BDAF) and ZIF-8 is respectively occurring at 450 DEG C and 400 DEG C, two kinds of materials earliest
Material shows excellent thermal stability, and the decomposition temperature of the compound PI-ZIF-10 of the two is similar to ZIF-8,400
DEG C decomposition takes place, this is because the ZIF-8 in compound takes the lead in caused by decomposing.
2. filter efficiency is tested
The air filtration performance of nano fibrous membrane is by fine particle content in the air before and after relevant nanometer Fibrous membrane filtration
Variation determines that (PM2.5 concentration is greater than the suitable test environment of burning cigarette construction by closed space in this test
200μg/m3), first using the PM2.5 concentration in aerosol detector measurement record air.Then, by institute PI-ZIF to be tested
Composite cellulosic membrane is placed in the air inlet of detector, guarantees enough leakproofness, subsequent register instrument reading will be filtered
The available filter efficiency of PM2.5 concentrations versus in PM2.5 concentration and air, measured filter efficiency are as shown in Fig. 6.
Attached drawing 6 shows that the filter efficiency of pure PI film is 83.2%, with the addition of ZIF-8, the filter efficiency of PI-ZIF film
It significantly improves, respectively 94.4%, 96.4%, 96.6%.This is mainly due to ZIF-8 to have high Zeta potential, surface
Charge can occur electrostatic interaction with the polar contaminants in air and improve so that PM particulate matter is adsorbed on fiber
The ability of fiber capture particulate matter.
In addition, the tunica fibrosa being also heat-treated to different temperatures after (100 DEG C, 200 DEG C, 300 DEG C, 1h) has also carried out filtering effect
The test of rate, as a result as shown in Fig. 7, after heat treatment the filter efficiency of tunica fibrosa and heat treatment before be consistent substantially, this into
One step confirms the high thermal stability of tunica fibrosa, even across being also able to maintain high filter efficiency after high temperature.
3. measuring mechanical property
The mechanical performance of nano fibrous membrane is assessed usually using tension test.By PI-ZIF composite cellulosic membrane in this test
It is cut into the strip of 2 × 15mm, it is fixed across in the u-bracket of papery and using glue to sample both ends, bracket two
Distance between arm is 5mm, then bracket two-arm is respectively fixed on two fixtures of test machine for mechanism or more, with 1mm/min's
Rate of extension is stretched, and load-displacement curves are obtained, and by assumed (specified) load/sectional area, displacement/sample original length can obtain fiber
The load-deformation curve of film, as shown in Fig. 8.
Attached drawing 8 shows to be added after ZIF-8, although the tensile strength of composite cellulosic membrane, elongation are integrally presented decline and become
Gesture, but since PI itself has excellent mechanical performance, the PI-ZIF composite membrane after reduction still has comparable intensity and elongation
Rate.In addition, the addition of ZIF-8 also improves the rigidity of tunica fibrosa, the initial stage is stretched, fiber is orientated in draw direction, deformation
It is easy, the modulus of PI and PI-ZIF-10 are respectively 6MPa and 4.7MPa, and subsequent fiber is arranged along draw direction, and deformation is difficult, PI
It increases separately with the modulus of PI-ZIF-10 to 10.7MPa and 29.2MPa, it is preferably anti-that this high modulus has fiber
Deformation, self-supporting ability.
4. pressure drop performance is tested
In nano fibrous membrane, the pressure drop of tunica fibrosa is as fiber to flowing through caused by the gas-flow resistance of tunica fibrosa.Pass through
The pressure drop of tunica fibrosa is the function of its thickness, fractional solid volume, air viscosity and superficial velocity.Fibre is flowed through with constant air-flow
Film is tieed up, the pressure difference of film two sides is measured using pressure difference instrument, measured pressure difference is pressure drop.By changing gas in this test
Body flow velocity draws out wind speed-falloff curve of tunica fibrosa, as shown in Fig. 9, by attached drawing 9 it can be seen that being added before and after ZIF-8,
The pressure drop of tunica fibrosa does not change substantially, this show the addition of ZIF-8 under the premise of not causing fiber resistance to increase, significantly
Improve the strainability of film.In addition, by being compared with two kinds of commercial filter films, it can be found that the pressure drop of all films is all situated between
In between the two, showing that tunica fibrosa meets the requirement to pressure drop of current commercial filter.
In conclusion composite cellulosic membrane multiple correlation produced by the present invention requires and has excellent performance.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (9)
1. a kind of preparation of metal organic frame-polyimide composite fiber membrane material, which comprises the following steps:
Step 1: the preparation of metal organic frame ZIF-8
A certain amount of methylimidazole and zinc nitrate are dissolved in methanol respectively, is stood for 24 hours after later mixing two solution, uses first
It is centrifugated after alcohol cleaning, it is dry to get ZIF-8；
Step 2: the preparation of soluble polyimide 6FDA-BDAF
(2.1) hexafluoropropane is dissolved in n,N-dimethylacetamide under the conditions of nitrogen and ice-water bath, it is complete to hexafluoropropane
Hexafluorodianhydride (6FDA) is added after dissolution into mixed liquor, obtains to contain solid mixed solution later containing solid mixed solution and persistently stirring 1h；
(2.2) solid mixed solution will be contained and remove ice-water bath, acid anhydrides and pyridine is added after persistently stirring 20h at room temperature, continues to stir
Viscosity solution is obtained after 20h；
(2.3) viscosity solution is poured into excessive dehydrated alcohol, obtains filament resin, dried after collecting filament resin to get solvable
Property polyimides 6FDA-BDAF；
Step 3: metal organic frame-polyimide composite fiber membrane material preparation
(3.1) metal organic frame ZIF-8 made from the step 1 is dissolved in n,N-dimethylacetamide, ultrasonic disperse 6h
After soluble polyimide 6FDA-BDAF made from the step 2 is added, until 1-3h is stirred at room temperature after being completely dissolved in it, obtain mixed
Close liquid；
(3.2) mixed liquor being moved into electrostatic spinning apparatus, aluminium foil is collector, it is arranged after electrospinning parameters through 1-2h electrospinning,
Take electrospinning film off later, as metal organic frame-polyimide composite fiber membrane material.
2. the preparation of metal organic frame according to claim 1-polyimide composite fiber membrane material, feature exist
In methylimidazole and zinc nitrate molar ratio in the step 1 are (2-8): 1.
3. the preparation of metal organic frame according to claim 1-polyimide composite fiber membrane material, feature exist
In, centrifugal rotational speed 10000rpm, centrifugation time 10min in the step 1, and cleaning-centrifugal process be repeated twice it is above.
4. the preparation of metal organic frame according to claim 1-polyimide composite fiber membrane material, feature exist
In the drying in the step 1 is to be placed in 120 DEG C of oven drying 12h.
5. a kind of preparation of metal organic frame-polyimide composite fiber membrane material according to claim 1, feature
It is, the hexafluoropropane in the step (2.1) is molten, the molar ratio of n,N-dimethylacetamide and hexafluorodianhydride (6FDA) is 1: 63: 1.
6. a kind of preparation of metal organic frame-polyimide composite fiber membrane material according to claim 1, feature
It is, by weight ratio meter, the acid anhydrides of the addition in the step (2.2) is the 7.9wt% containing solid solution, and pyridine is containing solid solution
The 6.2wt% of liquid.
7. a kind of preparation of metal organic frame-polyimide composite fiber membrane material according to claim 1, feature
It is, by weight ratio meter, the drying in the step (2.3) is to dry for 24 hours at 80 DEG C.
8. a kind of preparation of metal organic frame-polyimide composite fiber membrane material according to claim 1, feature
It is, soluble polyimide 6FDA-BDAF, metal organic frame ZIF-8, the N being added in the step (3.1), N- diformazan
The mass ratio of yl acetamide is 0.4: (0.01-0.04): 2.
9. a kind of preparation of metal organic frame-polyimide composite fiber membrane material according to claim 1, feature
It is, the technological parameter of coaxial electrically spun in the step (3.2) are as follows: receiver is 15cm, spinning with filator injection port distance
Voltage 15kV, ambient humidity < 40%, 20-30 DEG C of temperature.
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