CN107151862A - A kind of preparation method of high-efficiency nano fibre water-oil separationg film - Google Patents
A kind of preparation method of high-efficiency nano fibre water-oil separationg film Download PDFInfo
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- CN107151862A CN107151862A CN201610118578.6A CN201610118578A CN107151862A CN 107151862 A CN107151862 A CN 107151862A CN 201610118578 A CN201610118578 A CN 201610118578A CN 107151862 A CN107151862 A CN 107151862A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/0023—Electro-spinning characterised by the initial state of the material the material being a polymer melt
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/4334—Polyamides
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention is a kind of preparation method of high-efficiency nano fibre water-oil separationg film, including：Synthesizing polyamides acid (PAA), electrospinning PAA nano fibrous membranes and imines turn to polyimide film (PI)；Prepare cellulose acetate (CA) nano fibrous membrane；Simultaneously imines turns to CA PI to coaxial electrically spun CA PAA；Synthesize benzoxazine monomer (BAF btfa)；BAF btfa and BAF btfa/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA PI nano fibrous membranes；Contact angle experiments；Water-oil separating is tested.Advantage：By to fiber membrane surface modification, obtaining with biodegradability, CA PI nano fibrous membranes with low cost, with high water-oil separating flow and separative efficiency；This high performance membrane material has broad application prospects in the leakage of water-oil separating, sewage disposal and deep-sea oil.
Description
Technical field
The present invention relates to the preparation method of high-efficiency nano fibre water-oil separationg film, particularly one kind is driven for gravity
The preparation method of the efficient super-hydrophobic and super oleophylic electrostatic spinning water-oil separating tunica fibrosa of water-oil separating.
Background technology
Pass through electrostatic spinning, it has been reported that gone out many document such as polystyrene on nano fibrous membrane, polycaprolactone,
Polymethyl methacrylate, polyurethane and inorganic silicon dioxide fiber etc..But these fibers all exist separating rate it is slow,
Low separation efficiency, stability are poor, intensity difference, the shortcoming for easily producing secondary pollution.And separating rate is slow, separation
Efficiency is low, this maximum obstacle of intensity difference, seriously limits their applications in practice.
The content of the invention
Proposed by the present invention is a kind of to drive the efficient super-hydrophobic and super oleophylic Static Spinning silk oil of water-oil separating for gravity
Water separates the preparation method of tunica fibrosa, and its purpose is intended to the drawbacks described above for overcoming prior art to have, using CA and
PAA is raw material, by high voltage co-axial electrostatic spinning technique using the PAA of HMW as core, and CA is shell, is being passed through
Temperature programming to PAA carry out imidization obtain with biodegradability, it is with low cost, significantly separation flow, point
From the CA-PI nano fibrous membranes of efficiency and mechanical strength；By to tunica fibrosa surface modification, obtaining functional fiber
Membrane material；Moreover, this efficient super-hydrophobic super-oleophylic membrane material is in water-oil separating, sewage disposal and deep-sea oil
Had broad application prospects in leakage.
The technical solution of the present invention：The preparation method of efficient super-hydrophobic and super oleophylic water-oil separating nano fibrous membrane,
Comprise the technical steps that：
(1) synthesizing polyamides are sour (PAA)
(2) electrospinning PAA nano fibrous membranes and imines turn to polyimides (PI) film；
(3) cellulose acetate (CA) nano fibrous membrane is prepared；
(4) simultaneously imines turns to CA-PI films to coaxial electrically spun CA-PAA；
(5) synthesis benzoxazine monomer (BAF-btfa)；
(6) BAF-btfa and BAF-btfa/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PI
Nano fibrous membrane；
(7) contact angle experiments；
(8) water-oil separating is tested.
The positive effect of the present invention
A. there is high separation flow and separative efficiency, flow reaches 3106.2 ± 100L.m-2.h-1, separative efficiency reaches 99%
More than, improve 5-6 times compared to the water-oil separationg film flow that in the market is bought, it may have higher separative efficiency.
B. there is high mechanical strength and elongation at break, tensile strength and elongation at break respectively reach reach 120MPa and
More than 50%, compared to CA (shell)-PI of superhigh intensity, (core, monomer is 3,3,4,4- bibenzene tetracarboxylic dianhydrides (BPDA)
With p-phenylenediamine (PDA)) elongation strain of nano fibrous membrane, less than 20%, improved more than 3 times；And stretching should
Power is still able to reach 120MPa, compared to the tensile strength 6.65MPa of conventional CA nano fibrous membranes, improves
More than 20 times；
C. 144 ° only are can only achieve by the Maximum Contact angle of the BAF-btfa CA-PI nano fibrous membranes being modified and water, do not had
There is the property of super-hydrophobic and super oleophylic；And the maximum for passing through the modified CA-PI nano fibrous membranes of BAF-btfa and water connects
Feeler is up to 162 °, and oily contact angle can reach 0 °, the property with super-hydrophobic and super oleophylic, available for profit point
From process.
D. there is acid and alkali-resistance, resistant to elevated temperatures property, be still able to keep super-hydrophobic property under different pH and high temperature.
E. have can lasting usability, after storage 300 days, contact angle descends below 5%, by ten recyclings, flows
Amount is still able to reach 2700 ± 100L m-2h-1Left and right, separative efficiency reaches 99%.
F. high pressure can be born, the maximum pressure that can bear can reach 0.78kPa.
Brief description of the drawings
Fig. 1 is the structural representation of electrospinning PAA nanofiber film devices.
Fig. 2 is the process schematic of coaxial electrically spun CA-PI nano fibrous membranes.
Fig. 3 is to place contacts of 300 days F-PBZ-1/SNP-4/PI and F-PBZ-1/SNP-4/CA-PI with water at room temperature
Angle variation diagram.
Fig. 4 be different pH and at a temperature of, the contact angle variation diagram of F-PBZ-1/SNP-4/CA-PI and water
Fig. 5 is the BAF-btfa of various concentrations, BAF-btfa/SiO2CA, PI, CA-PI film, are followed after NPs in-situ solidifyings
Ring is different types of using 10 F-PBZ-1/SNP-4/CA-PI films and F-PBZ-1/SNP-4/CA-PI UF membranes
The flow and separative efficiency figure of oil water mixture.
Fig. 6 is that the flow of F-PBZ-1/SNP-4/CA-PI UF membranes dichloromethane-aqueous mixtures of different-thickness and separation are imitated
Rate figure and their porosity figure.
Embodiment
The preparation method of the preparation method of efficient super-hydrophobic and super oleophylic water-oil separating nano fibrous membrane, including following work
Skill step：
(1) PAA is synthesized；
Bibenzene tetracarboxylic is added in the drying four-hole boiling flask for exporting pipe equipped with mechanical agitator, thermometer, nitrogen
2.9422 and 2.0024g (mol ratio 1: 1) mixing is equal respectively for dianhydride (BPDA) and 2,4- diaminodiphenyl ether (ODA)
It is even；Under strong mechanical agitation, 40ml DMAc are added, after being reacted 24h hours at -15 DEG C -5 DEG C, then
Terminate reaction, obtain PAA, and its molecular weight is tested using gel permeation chrommatograph (Agilent).
(2) electrospinning PAA nano fibrous membranes and imines turn to polyimides (PI) film：
With 1-5% (wt) PAA DMAc solution, the spinning in voltage is 30Kv (+20, -10Kv) high-voltage electrostatic field,
The reception distance of syringe needle point to flywheel is 10-15cm, and the rotating speed of flywheel turns/min for 1000-2000, electrospinning
Speed is 0.5-1ml/h, is spun to polyamic acid (PAA) nano fibrous membrane, as shown in Figure 1.By the good PAA of electrospinning
Nano fibrous membrane is according to 150 DEG C/1h of temperature programming, 200 DEG C/1h, 250 DEG C/1h, 300 DEG C/1h, 350 DEG C/3h,
380 DEG C/30mim method carries out imidization in tube furnace and obtains PI films；The omnipotent material newly thought carefully with Shenzhen afterwards
Material testing machine (CMT-8500 types) is tested the stress-strain of PI films at room temperature, tests its stress-strain.
(3) preparation of CA nano fibrous membranes
The preparation of CA nano fibrous membranes：With the mixed solution of 5-10% (wt) dichloromethane and acetone (2/1 (V/V)),
The spinning in high-voltage electrostatic field, the distance of syringe needle point to roller is 10-15cm, and electrospinning speed is 0.5-1ml/h,
CA nano fibrous membranes are spun to, electric spinning equipment is with the device of electrospinning PAA films, obtained nano fibrous membrane Shenzhen
The universal testing machine (CMT-8500 types) newly thought carefully carries out test stress-strain at room temperature.
(4) simultaneously imines turns to CA-PI to coaxial electrically spun CA-PAA：
The preparation of coaxial CA-PAA nano fibrous membranes：It is that coaxial syringe needle is used on the basis of traditional electric spinning equipment,
1-5% (wt) PAA DMAc solution is used as core, 5-10% (wt) dichloromethane and mixing for acetone 2: 1 (V/V)
Solution is closed as shell, the spinning in high-voltage electrostatic field, rotatably flywheel carries out receiving CA-PAA nanofibers at a high speed.
By the good CA-PAA nano fibrous membranes of electrospinning according to 150 DEG C of temperature programming/2h, 200/3h, 250 DEG C/1h, 260 DEG C/1h
Method carry out imidization obtain CA-PI nano fibrous membranes；Obtained nano fibrous membrane uses ten thousand that Shenzhen is newly thought carefully
Can Material Testing Machine (CMT-8500 types) progress test stress-strain at room temperature.As shown in Figure 2.
(5) benzoxazine monomer is synthesized
1) by bisphenol AF, paraformaldehyde and 2,5- bis trifluoromethyls aniline difference 16.8115g, 6g and 22.912g,
Sequentially add equipped with condensing reflux pipe, electric blender, N2In airway tube, the four-hole bottle of thermometer；
2) it is difficult that question response thing is cooled to room temperature untill stirring that heating is sticky until reactant, and CHCl is added to it3
200ml is dissolved；The complete mixed solution of above-mentioned dissolving is washed with the NaOH solution of mass fraction 2%, treats molten
A layer solution is removed in liquid layering.The solution separated is added to 50ml CHCl3；Uniform rear addition 2g to be mixed
Anhydrous calcium chloride (CaCl2) dehydration；Solution after dehydration is dried, fluorine-containing benzoxazine (BAF-btfa) is obtained
Monomer powders.
(6) BAF-btfa and BAF-btfa/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PI
Nano fibrous membrane；
1) 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, 0.1g and 0.4g BAF-btfa monomer powder are weighed
End, is respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% to be dissolved according to mass fraction
In butyl acetate, the clear solution that dissolving is complete and mixing is homogeneous is obtained；
2) CA, PI, CA-PI tunica fibrosa of preparation are cut into 2 × 2cm width and the laboratory sample of length, and should
Tunica fibrosa is immersed in the butyl acetate solution dissolved with BAF-btfa；
3) with take the photograph son CA, PI, CA-PI tunica fibrosa being immersed in mixed solution are taken out rapidly, first in natural bar
Dried under part, then put vacuum into and solidified for case；Be cooled to room temperature afterwards, take out F-PBZ/CA, F-PBZ/PI,
F-PBZ/CA-PI is standby.
4) 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, 0.1g and 0.4g BAF-btfa monomers are weighed
Powder, is respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% dissolving according to mass fraction
In butyl acetate；
5) and add mass fraction be 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% SiO2
NPs obtains the clear solution that dissolving is complete and mixing is homogeneous into butyl acetate solution；
6) CA, PI, CA-PI tunica fibrosa of preparation are cut into 2 × 2cm width and the laboratory sample of length, and should
Tunica fibrosa is immersed in dissolved with BAF-btfa and SiO2In NPs butyl acetate liquid；Finally, it will be immersed in tweezers mixed
The tunica fibrosa closed in solution takes out rapidly, first dries under field conditions (factors), then puts vacuum drying oven into and carries out solidification 2h,
Room temperature is cooled to afterwards, takes out F-PBZ/SNP/CA, F-PBZ/SNP/PI, F-PBZ/SNP/CA-PI standby.
(7) contact angle experiments
Using contact angle experiments instrument to various concentrations BAF-btfa and SiO2CA, PI, CA-PI that NPs is modified
Nano fibrous membrane, F-PBZ/CA, F-PBZ/PI, F-PBZ/CA-PI and F-PBZ/SNP/CA, F-PBZ/SNP/PI,
The hydrophobic performance of sample obtained by each above-mentioned concentration of F-PBZ/SNP/CA-PI composite cellulosic membranes and oleophylic performance
Static contact angle is studied.
(8) water-oil separating is tested
1) 10ml dichloromethane and water is measured respectively,
Water methylene blue staining, oily (dichloromethane) is dyed with oil red.By 200ml oil mixing with water solution left standstill 1min
Afterwards, profit is separated.The water of blueness is dyed on upper strata, red oil is in lower floor, F-PBZ-1/SNP-4/CA-PI
Functional fibre film is fixed between two glass tubes.Then, the mixed solution of layering is poured into glass tube above,
Carry out water-oil separating.Red oil rapidly permeates F-PBZ-1/SNP-4/CA-PI tunica fibrosas, flows to following beaker
In, and the water of blueness is still remained in the glass tube on upper strata, and record profit completely isolated time, and measurement
With the volume of water after separation before separation.
2) different oil water mixture (dichloromethane-water, bromobenzene-water, carbon tetrachloride-water, three chloromethanes are selected respectively
Alkane-water and 1,2- dichloroethanes-water) 20ml (1/1 (V/V)), according to 1) progress water-oil separating experiment.
3) the CA-PAA films of electrospinning different-thickness and imidization obtain CA-PI films respectively, by 1wt%'s
BAF-btfa and 4wt%SiO2NPs in-situ solidifyings obtain different-thickness F-PBZ-1/SNP-4/CA-PI films.And by 1)
Carry out water-oil separating experiment.
4) F-PBZ-1/SNP-4/CA-PI films are selected, and by 1) the multiple water-oil separating of progress.
(9) the maximum pressure experiment that F-PBZ-1/SNP-4/CA-PI films can bear.
Selection height is 10cm, and 15cm, 20cm, 30cm, 40cm glass tube, water pours into glass tube above
It is interior, the maximum weight that record water can not be flowed in following beaker.
Of the invention main is exactly that coaxial electrically spun obtains coaxial CA-PI nano fibrous membranes, the use BAF-btfa done before with
SiO2The CA that NPs is modified, because its stress 6.65MPa can not carry out water-oil separating with method as shown in Figure 1
Experiment；BAF-btfa and SiO2The PI that NPs is modified, its flow and separative efficiency also can only achieve 450 ± 100L m-2
h-1With 99%.The CA-PI nano fibrous membranes of the super-hydrophobic super-oleophylic of the existing high intensity of research before me, although
Its intensity reaches is higher than 200MPa, but during actual water-oil separating use, pliability is still that one should
The problem of attention, the elongation strain of the CA-PI nano fibrous membranes of early-stage Study high intensity is being advised greatly less than 15%
Some obstacles can be run into during mould use unavoidably.This requires we find out a kind of fabulous relative stretching of pliability strong
The water-oil separating that degree and high material are used in practical application.Herein, we pass through a kind of new high-flexibility
Polyimides as core, electrospinning is into coaxial CA-PI nano fibrous membranes, and this is like poor in mechanical property
CA inside plus good steel wire of pliability, its final elongation strain is up to 50%, and stress is up to 120MPa,
The BAF-btfa and SiO after high temperature imidization2The CA-PI films that NPs is modified, its flow can reach 3106 ±
100L m-2h-1, separative efficiency reaches 99.7%.And can acid-fast alkali-proof, high temperature resistant uses for recyclable 10 times,
This can not only improve CA mechanical property, and it is soft in actual water-oil separating application to overcome existing electrospinning film
Poor toughness, matter are crisp, not durable in use, and flow is low, low separation efficiency, poor mechanical property, in the mistake of recycling
The shortcoming for being particularly easy to brokenly and easily being corroded by strong acid, highly basic and high temperature harsh conditions in journey.Add existing
The usable number of times of water-oil separationg film, has saved financial cost.
Claims (8)
1. the preparation method of high-efficiency nano fibre water-oil separationg film, it is characterized in that comprising the technical steps that：
(1) synthesizing polyamides are sour (PAA)
(2) electrospinning PAA nano fibrous membranes and imines turn to polyimides (PI) film；
(3) cellulose acetate (CA) nano fibrous membrane is prepared；
(4) simultaneously imines turns to CA-PI to coaxial electrically spun CA-PAA；
(5) synthesis benzoxazine monomer (BAF-btfa)；
(6) BAF-btfa and BAF-btfa/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PI
Nano fibrous membrane；
(7) water-oil separating is tested.
2. the preparation method of high-efficiency nano fibre water-oil separationg film according to claim 1, it is characterized in that described step
(1) synthesizing polyamides are sour (PAA)：The drying four-hole boiling flask into pipe is being exported equipped with mechanical agitator, thermometer, nitrogen
2.9422 and 2.0024g of middle addition bibenzene tetracarboxylic dianhydride (BPDA) and 2,4- diaminodiphenyl ether (ODA) difference (mole
Than 1: 1), be well mixed；Under strong mechanical agitation, DMAc 40ml are added, 24h is reacted at -15 DEG C -5 DEG C
After hour, then terminate reaction, obtain polyamic acid.
3. the preparation method of high-efficiency nano fibre water-oil separationg film according to claim 1, it is characterized in that described step
(2) preparation of PAA nano fibrous membranes and imines turn to polyimides (PI) film：With 1-5% (wt) PAA DMAc
Solution, the spinning in voltage is 30Kv (+20, -10KV) high-voltage electrostatic field, the reception of syringe needle point to flywheel away from
Turn/min from the rotating speed for 10-15cm, flywheel for 1000-2000, the speed of electrospinning is 0.5-1ml/h, is spun to PAA
Nano fibrous membrane.By the good PAA nano fibrous membranes of electrospinning according to 150 DEG C/1h of temperature programming, 200 DEG C/1h, 250 DEG C/1h,
300 DEG C/1h, 350 DEG C/3h, 380 DEG C/30min method carries out imidization in tube furnace and obtains PI films；Afterwards with deep
The universal testing machine (CMT-8500 types) that ditch between fields is newly thought carefully is strained to the stress one of PI films to be tested at room temperature,
Test its stress-strain.
4. the preparation method of high-efficiency nano fibre water-oil separationg film according to claim 1, it is characterized in that described step
(3) preparation of CA nano fibrous membranes：With the mixed solution of 5-10% (wt) dichloromethane and acetone (2/1 (V/V)),
The spinning in high-voltage electrostatic field, the distance of syringe needle point to roller is 10-15cm, and electrospinning speed is 0.5-1ml/h, spinning
Into CA nano fibrous membranes, electric spinning equipment is with the device of electrospinning PAA films, and obtained nano fibrous membrane Shenzhen is newly thought carefully
Universal testing machine (CMT-8500 types) carry out test stress-strain at room temperature.
5. it is according to claim 1, it is characterized in that described step (4) coaxial electrically spun CA (shell)-PAA (core) is simultaneously
Imines turns to the preparation of CA-PI tunica fibrosas：It is that coaxial syringe needle, 1-5% are used on the basis of traditional electric spinning equipment
(wt) PAA DMAc solution is used as core, 5-10% (wt) dichloromethane and the mixed solution of acetone 2: 1 (V/V)
As shell, the spinning in high-voltage electrostatic field, rotatably flywheel carries out receiving CA-PAA nanofibers at a high speed.Electrospinning is good
CA-PAA nano fibrous membranes are carried out according to 150 DEG C of temperature programming/2h, 200/3h, 250 DEG C/1h, 260 DEG C/1h method
Imidization obtains CA-PI nano fibrous membranes；Obtained nano fibrous membrane uses the universal testing machine that Shenzhen is newly thought carefully
(CMT-8500 types) carries out test stress one and strained at room temperature.
6. the preparation method of high-efficiency nano fibre water-oil separationg film according to claim 1, it is characterized in that described step
(5) benzoxazine monomer is synthesized：
1) by bisphenol AF, paraformaldehyde and 2,5- bis trifluoromethyls aniline distinguishes 16.8115,6 and 22.912g, sequentially adds
Equipped with condensing reflux pipe, electric blender, N2In airway tube, the four-hole bottle of thermometer；
2) it is difficult that question response thing is cooled to room temperature untill stirring that heating is sticky until reactant, and CHCl is added to it3200ml enters
Row dissolving；
3) the complete mixed solution of above-mentioned dissolving is washed with the NaOH solution of mass fraction 2%, treats that a layer solution is removed in solution layering.
The solution separated is added to 50ml CHCl3；
4) the uniform rear anhydrous calcium chloride (CaCl for adding 2g to be mixed2) dehydration；
5) solution after dehydration is dried, obtains fluorine-containing benzoxazine (BAF-btfa) monomer powders.
7. the preparation method of high-efficiency nano fibre water-oil separationg film according to claim 1, it is characterized in that described step
(6) BAF-btfa and BAF-btfa/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PI
Nano fibrous membrane；
1) 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, 0.1g and 0.4g fluorine-containing benzoxazine BAF-btfa are weighed
Monomer powders, are respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% molten according to mass fraction
Solution obtains the clear solution that dissolving is complete and mixing is homogeneous in butyl acetate；
2) CA, PI, CA-PI tunica fibrosa of preparation is cut into 2 × 2cm width and the laboratory sample of length, and by the fibre
Film immersion is tieed up in the butyl acetate solution dissolved with fluorine-containing benzoxazine BAF-btfa；
3) with take the photograph son CA, PI, CA-PI tunica fibrosa being immersed in mixed solution are taken out rapidly, first in natural conditions
Under dry, then put vacuum into and solidified for case；Be cooled to room temperature afterwards, take out F-PBZ/CA, F-PBZ/PI,
F-PBZ/CA-PI is standby.
4) 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, 0.1g and 0.4g BAF-btfa monomer powders are weighed,
It is respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% to be dissolved in acetic acid fourth according to mass fraction
In ester；
5) and add mass fraction be 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% SiO2NPs
Into butyl acetate solution, the clear solution that dissolving is complete and mixing is homogeneous is obtained；
6) CA, PI, CA-PI tunica fibrosa of preparation is cut into 2 × 2cm width and the laboratory sample of length, and by the fibre
Film immersion is tieed up dissolved with BAF-btfa and SiO2In NPs butyl acetate liquid；Finally, mixed solution will be immersed in tweezers
In tunica fibrosa take out rapidly, first dry under field conditions (factors), then put into vacuum drying oven carry out solidification 2h, be cooled to afterwards
Room temperature, takes out F-PBZ/SNP/CA, F-PBZ/SNP/PI, F-PBZ/SNP/CA-PI standby.
8. the preparation method of high-efficiency nano fibre water-oil separationg film according to claim 1, it is characterized in that described step
(7) water-oil separating is tested：
1) 10ml dichloromethane and water is measured respectively,
Water methylene blue staining, oily (dichloromethane) is dyed with oil red.After 200ml oil mixing with water solution left standstill 1min,
Profit is separated.The water of blueness is dyed on upper strata, red oil is in lower floor, and F-PBZ-1/SNP-4/CA-PI functions are fine
Dimension film is fixed between two glass tubes.Then, the mixed solution of layering is poured into glass tube above, carries out profit
Separation.Red oil rapidly permeates F-PBZ-1/SNP-4/CA-PI tunica fibrosas, flows in following beaker, and blueness
Water is still remained in the glass tube on upper strata, and is recorded before profit completely isolated time, and measurement separation and after separation
The volume of water.
2) select respectively different oil water mixture (dichloromethane-water, bromobenzene-water, carbon tetrachloride-water, chloroform-
Water and 1,2- dichloroethanes-water) 20ml (1/1 (V/V)), according to 1) progress water-oil separating experiment.
3) the CA-PAA films of electrospinning different-thickness and imidization obtain CA-PI films respectively, in the BAF-btfa by 1wt%
And 4wt%SiO2NPs in-situ solidifyings obtain different-thickness F-PBZ-1/SNP-4/CA-PI films.And by 1) progress profit
Separating experiment.
4) F-PBZ-1/SNP-4/CA-PI films are selected, and by 1) the multiple water-oil separating of progress.
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