CN105603637A - Efficient electrostatic spinning oil-water separation fiber membrane - Google Patents
Efficient electrostatic spinning oil-water separation fiber membrane Download PDFInfo
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- CN105603637A CN105603637A CN201610040433.9A CN201610040433A CN105603637A CN 105603637 A CN105603637 A CN 105603637A CN 201610040433 A CN201610040433 A CN 201610040433A CN 105603637 A CN105603637 A CN 105603637A
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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
- D04H1/425—Cellulose series
- D04H1/4258—Regenerated cellulose series
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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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
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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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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- 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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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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
Abstract
The invention discloses a preparation method of an efficient electrostatic spinning oil-water separation fiber membrane. The preparation method includes the steps that polyamic acid (PPA) is synthesized, a PPA nanofiber membrane is prepared in an electrospinning mode, and the PPA nanofiber membrane is imidized into a polyimide membrane (PI); a cellulose acetate (CA) nanofiber membrane is prepared; coaxial electrospinning is carried out on CA-PAA, and a product is imidized into CA-PI; benzoxazine monomers (BAF-tfa) are synthesized; in-situ immobilization is performed on the CA, PI and CA-PI nanofiber membranes with BAF-tfa and BAF-tfa/silica nanoparticles (SiO2NPs); an oil-water separation experiment is carried out. The preparation method has the advantages that by carrying out surface modification on the fiber membranes, the CA-PI nanofiber membrane which is biodegradable, low in cost, large in oil-water separation flow and high in separation efficiency is obtained; the high-performance membrane material has broad application prospects in oil-water separation, sewage treatment and deepwater oil leak.
Description
Technical field
That the present invention relates to is a kind of preparation method of efficient electrostatic spinning water-oil separating tunica fibrosa, particularly a kind of usingOrder about the preparation side of the efficient super-hydrophobic and super oleophylic electrostatic spinning water-oil separating tunica fibrosa of water-oil separating in gravityMethod.
Background technology
By electrostatic spinning, report out such as polystyrene of many documents about nano fibrous membrane, polycaprolactone,Polymethyl methacrylate, polyurethane and inorganic silicon dioxide fiber etc. But these fibers all exist separating rate slow,Separative efficiency is low, poor stability, intensity difference, easily produce the shortcoming of secondary pollution. And separating rate is slow, separationEfficiency is low, and this maximum obstacle of intensity difference, has seriously limited their application in practice.
Summary of the invention
What the present invention proposed is a kind of efficient super-hydrophobic and super oleophylic Static Spinning silk oil that orders about water-oil separating for gravityWater separates the preparation method of tunica fibrosa, and its object is intended to overcome the above-mentioned defect that prior art has, adopt CA andPAA is raw material, and by high pressure coaxial electrostatic spinning technology, taking the poly-PAA of HMW as core, CA is shell, at warpCross temperature programming to PAA carry out imidization obtain thering is biodegradability, with low cost, significantly separate flux,The CA-PI nano fibrous membrane of separative efficiency and mechanical strength; By to tunica fibrosa finishing, obtain functional fibreDimension membrane material; And this super-hydrophobic super oil-wet film material is efficiently at water-oil separating, sewage disposal and deep-sea stoneOil has broad application prospects in leaking.
Technical solution of the present invention: the preparation method of super-hydrophobic and super oleophylic water-oil separating nano fibrous membrane efficiently,Comprise following processing step:
(1) synthesizing polyamides acid (PAA)
(2) electrospinning PAA nano fibrous membrane and imines turn to polyimides (PI) film;
(3) prepare cellulose acetate (CA) nano fibrous membrane;
(4) coaxial electrically spun CA-PAA imines turn to CA-PI;
(5) synthetic benzoxazine monomer (BAF-tfa);
(6) BAF-tfa and BAF-tfa/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PINano fibrous membrane;
(7) contact angle experiments
(8) water-oil separating experiment.
Good effect of the present invention
A. have high separation flow and separative efficiency, flow reaches 2270Lm-2h-1, separative efficiency reaches more than 99%,Compare the water-oil separating film flow of buying on market and improved 3-4 doubly, also there is higher separative efficiency.
B. there is high intensity, more than hot strength reaches 200MPa, compare the hot strength of conventional CA nano fibrous membrane6.65MPa, has improved more than 30 times;
C. only can only reach 137 °, not tool through the CA-PI nano fibrous membrane of BAF-tfa modification and the Maximum Contact angle of waterThere is super-hydrophobic and super close oil properties; And the maximum of CA-PI nano fibrous membrane and water connects after BAF-tfa modificationFeeler can reach 161 °, and the contact angle of oil can reach 0 °, has super-hydrophobic and super close oil properties, can be used for profit and dividesFrom process.
D. there is acid and alkali-resistance, resistant to elevated temperatures character, under different pH and high temperature, still can keep super-hydrophobic character.
E. there is usability lastingly, deposit after 300 days, under contact angle, be reduced to 5%, recycle through ten times, streamAmount still can reach 2000Lm-2h-1Left and right, separative efficiency reaches 98.5%.
Brief description of the drawings
Fig. 1 is the structural representation of electrospinning PAA nanofiber film device.
Fig. 2 is the process schematic diagram of coaxial electrically spun CA-PI nano fibrous membrane.
Fig. 3 is the contact angle variation diagram of at room temperature placing 300 days F-PBZ-1/PI and F-PBZ-1/CA-PI and water.
Fig. 4 is at different pH and temperature, the contact angle variation diagram of F-PBZ-1/SNP-4/CA-PI and water.
Fig. 5 is BAF-tfa and the BAF-tfa/SiO of variable concentrations2CA, PI, CA-PI flow after NPs in-situ solidifyingWith separative efficiency figure.
Fig. 6 is different types of oil mixing with water logistics capacity and separative efficiency figure; Recycle 10 timesF-PBZ-1/SNP-4/CA-PI flow and separative efficiency variation diagram and BAF-tfa/SiO2NPs in-situ solidifying difference is thickFlow and separative efficiency figure after the CA-PI of degree.
Fig. 7 is the porosity change figure of the CA-PI of different-thickness.
Detailed description of the invention
The preparation method's of super-hydrophobic and super oleophylic water-oil separating nano fibrous membrane preparation method, comprises following work efficientlySkill step:
(1) synthetic PAA;
In the dry four-hole boiling flask that mechanical agitator, thermometer, nitrogen are housed derive pipe, add bibenzene tetracarboxylicDianhydride (BPDA) and p-phenylenediamine (PPD) (PDA) difference 2.9422 and 1.0814g (mol ratio 1: 1) mix; By forceUnder strong mechanical agitation, add 40mlDMAc, at-15 DEG C-5 DEG C, react after 24h hour, finish subsequently reaction,Obtain PAA.
(2) electrospinning PAA nano fibrous membrane and imines turn to polyimides (PI) film:
With the DMAc solution of 1-5% (wt) PAA, be spinning in the high-voltage electrostatic field of 30Kv (+20 ,-10KV) at voltage,Syringe needle point is 10-15cm to the receiving range of flywheel, and the rotating speed of flywheel is turn/min of 1000-2000, electrospinningSpeed is 0.5-1ml/h, is spun to polyamic acid (PAA) nano fibrous membrane, as shown in Figure 1. By the good PAA of electrospinningNano 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/30mimMethod in tube furnace, carry out imidization and obtain PI film; The universal testing machine of newly thinking carefully with Shenzhen afterwards(CMT-8500 type) at room temperature tested stress one strain of PI film, tests its stress-strain.
(3) preparation of CA nano fibrous membrane,
The preparation of CA nano fibrous membrane: with the carrene of 5-10% (wt) and the mixed solution of acetone (2/1 (V/V)),Spinning in high-voltage electrostatic field, syringe needle point is 10-15cm to the distance of cylinder, electrospinning speed is 0.5-1ml/h,Be spun to CA nano fibrous membrane, electric spinning equipment is with the device of electrospinning PAA film, and the nano fibrous membrane obtaining is used ShenzhenThe universal testing machine (CMT-8500 type) of newly thinking carefully at room temperature carries out test stress-strain.
(4) coaxial electrically spun CA-PAA imines turn to CA-PI:
The preparation of coaxial CA-PAA nano fibrous membrane: be on the basis of traditional electric spinning equipment, to adopt coaxial syringe needle,The DMAc solution of 1-5% (wt) PAA is as core, and the carrene of 5-10% (wt) and acetone 2: 1 (V/V) mixesClose solution as shell, spinning in high-voltage electrostatic field, High Rotation Speed ground flywheel receives CA-PAA nanofiber.By CA-PAA nano fibrous membrane good electrospinning according to 150 DEG C/2h of temperature programming, 200/3h, 250 DEG C/1h, 260 DEG C/1hMethod carry out imidization and obtain CA-PI nano fibrous membrane; The nano fibrous membrane that obtains adopt that Shenzhen newly thinks carefully ten thousandCan Material Testing Machine (CMT-8500 type) at room temperature carry out test stress one strain. As shown in Figure 2.
(5) synthetic benzoxazine monomer
1) by bisphenol A/F, paraformaldehyde and m-benzotrifluoride amine difference 14.7,5.3 and 14.1g, add and be equipped with successivelyCondensing reflux pipe, electric blender, N2In the four-hole bottle of wireway, thermometer;
2) heating is until reactant thickness is difficult to stir, and question response thing is cooled to room temperature, adds CHCl to it3200ml dissolves; With the above-mentioned dissolving of the NaOH solution washing mixed solution completely of mass fraction 2%, treat moltenA layer solution is taken off in liquid layering. The solution of separating is added to the CHCl of 50ml3; After stirring, add 2gAnhydrous calcium chloride (CaCl2) dehydration; Solution after dehydration is dried, obtains the monomer powders of fluorine-containing benzoxazine.(6) BAF-tfa and BAF-tfa/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PINano fibrous membrane;
1) take 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, the fluorine-containing benzoxazine of 0.1g and 0.4gBAF-tfa monomer powders, according to mass fraction be respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%,4.0% is dissolved in butyl acetate (ButylAcetate), obtains dissolving completely and mix the clear solution of homogeneous;
2) by the laboratory sample of CA, PI, CA-PI tunica fibrosa cutting 2 × 2cm width and the length of preparation, and shouldTunica fibrosa is immersed in the butyl acetate solution that is dissolved with fluorine-containing benzoxazine BAF-tfa;
3) with taking the photograph son, CA, the PI, the CA-PI tunica fibrosa that are immersed in mixed solution are taken out rapidly, first at natural barUnder part, dry, then put vacuum into and be cured for case; Be cooled to afterwards room temperature, taking-up F-PBZ/CA, F-PBZ/PI,F-PBZ/CA-PI is for subsequent use.
4) take 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, the BAF-tfa monomer powders of 0.1g and 0.4g, pressesBe respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% according to mass fraction and be dissolved in acetic acid fourthIn ester (ButylAcetate);
5) and to add mass fraction be 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% SiO2NPs, in butyl acetate solution, obtains dissolving completely and mixes the clear solution of homogeneous;
6) by the laboratory sample of CA, PI, CA-PI tunica fibrosa cutting 2 × 2cm width and the length of preparation, and shouldTunica fibrosa is immersed in and is dissolved with BAF-tfa and SiO2In the butyl acetate liquid of NPs; Finally, will be immersed in mixing with tweezersTunica fibrosa in solution takes out rapidly, first dries under field conditions (factors), and then put vacuum drying oven into and be cured 2h, itAfter be cooled to room temperature, take out F-PBZ/SNP/CA, F-PBZ/SNP/PI, F-PBZ/SNP/CA-PI for subsequent use.
(7) contact angle experiments,
Utilize the CA of contact angle experiments instrument to different concentration benzoxazines and Nano particles of silicon dioxide modification,PI, CA-PI 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 the sample that above-mentioned each concentration of F-PBZ/SNP/CA-PI composite cellulosic membrane obtainsStudy with the static contact angle of oleophylic performance.
(8) water-oil separating experiment:
1) measure respectively carrene and the water of 10ml,Water methylene blue staining, oil (carrene) dyes with oil red. By the oil mixing with water solution left standstill 1min of 200mlAfter, profit separates. Be dyed to blue water on upper strata, red oil is in lower floor, F-PBZ--1/SNP-4/CA-PIFunctional fibre film is fixed between two glass tubes. Then, the mixed solution of layering is poured in glass tube above,Carry out water-oil separating. Red oil permeates F-PBZ-1/SNP-4/CA-PI tunica fibrosa rapidly, flows to beaker belowIn, and blue water is still stayed in the glass tube on upper strata, and record the time that profit is separated completely, and measureSeparate the front volume with separating rear water.
2) select respectively different oil water mixtures (carrene-water, bromobenzene-water, carbon tetrachloride-water, three chloromethanesAlkane-water and 1,2-dichloroethanes-water) 20ml (1/1 (V/V)), according to 1) carry out water-oil separating experiment.
3) the CA-PAA film of electrospinning different-thickness imidization obtain CA-PI film respectively, process 1wt%'sBAF-tfa and 4wt%SiO2NPs in-situ solidifying obtains different-thickness F-PBZ-1/SNP-4/CA-PI film. And by 1)Carry out water-oil separating experiment.
4) select F-PBZ-1/SNP-4/CA-PI film, and by 1) carry out repeatedly water-oil separating.
The present invention is exactly mainly that coaxial electrically spun obtains coaxial CA-PI nano fibrous membrane, do before with BAF-tfa andSiO2The CA of NPs modification, its flow can only reach 1800Lm-2h-1, separative efficiency reaches 96%, stress6.65MPa; BAF-tfa and SiO2The PI of NPs modification, its flow and separative efficiency also can only reach 400Lm-2h-1With 95%, and we become coaxial CA-PI nano fibrous membrane to electrospinning when doing, just look like at mechanical performance comparePoor CA the inside adds a steel wire, through BAF-tfa and SiO after high temperature imidization2The CA-PI of NPs modificationFilm, its flow can reach 2270Lm-2h-1, separative efficiency reaches 99.5%, improves its strain and is greater than 200MPa.And can acid-fast alkali-proof, high temperature resistant, use for 10 times capable of circulation, in the application of actual water-oil separating, Neng Gou greatThe large time of saving water-oil separating, cost-saving. Overcome existing electrospinning film stream in actual water-oil separating applicationMeasure lowly, separative efficiency is low, and poor mechanical property is not durable in use, especially easy broken appearance in the process recyclingEasily by strong acid, the shortcoming of highly basic and the corrosion of high temperature harsh conditions. Increase using of existing water-oil separating film inferiorNumber, has saved financial cost.
Claims (8)
1. the preparation method of efficient electrostatic spinning water-oil separating tunica fibrosa, is characterized in that comprising following processing step:
(1) synthesizing polyamides acid (PAA)
(2) electrospinning PAA nano fibrous membrane and imines turn to polyimides (PI) film;
(3) prepare cellulose acetate (CA) nano fibrous membrane;
(4) coaxial electrically spun CA-PAA imines turn to CA-PI;
(5) synthetic benzoxazine monomer (BAF-tfa);
(6) BAF-tfa and BAF-tfa/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PI receiveRice tunica fibrosa;
(7) water-oil separating experiment.
2. the preparation method of efficient electrostatic spinning water-oil separating tunica fibrosa according to claim 1, described in it is characterized in thatStep (1) synthesizing polyamides acid (PAA); Being housed, mechanical agitator, thermometer, nitrogen derive into dry four of pipeIn mouth flask, add bibenzene tetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PPD) (PDA) difference 2.9422 and 1.0814g (mol ratio1: 1), mix; Under strong mechanical agitation, add DMAc40ml, at-15 DEG C-5 DEG C, react 24h hourAfter, finish subsequently reaction, obtain polyamic acid.
3. the preparation method of efficient electrostatic spinning water-oil separating tunica fibrosa according to claim 1, described in it is characterized in thatPreparation and the imines of step (2) PAA nano fibrous membrane turn to polyimides (PI) film: with 1-5% (wt) PAADMAc solution, be spinning in the high-voltage electrostatic field of 30Kv (+20 ,-10KV) at voltage, syringe needle point is to flywheelReceiving range is 10-15cm, and the rotating speed of flywheel is turn/min of 1000-2000, and the speed of electrospinning is 0.5-1ml/h, spinningBecome PAA nano fibrous membrane. By PAA nano fibrous membrane good electrospinning according to 150 DEG C/1h of temperature programming, 200 DEG C/1h,250 DEG C/1h, 300 DEG C/1h, the method for 350 DEG C/30mim is carried out imidization and is obtained PI film in tube furnace; Use afterwards darkThe universal testing machine (CMT-8500 type) that ditch between fields is newly thought carefully is at room temperature tested stress one strain of PI film,Test its stress-strain.
4. the preparation method of efficient electrostatic spinning water-oil separating tunica fibrosa according to claim 1, described in it is characterized in thatThe preparation of step (3) CA nano fibrous membrane: with the carrene of 5-10% (wt) and mixing of acetone (2/1 (V/V))Close solution, spinning in high-voltage electrostatic field, syringe needle point is 10-15cm to the distance of cylinder, electrospinning speed is0.5-1ml/h, is spun to CA nano fibrous membrane, and electric spinning equipment is with the device of electrospinning PAA film, the nano fibrous membrane obtainingThe universal testing machine (CMT-8500 type) of newly thinking carefully with Shenzhen at room temperature carries out test stress-strain.
5. according to claim 1, it is characterized in that described step (4) coaxial electrically spun CA (shell)-PAA (core) alsoThe preparation method of the efficient electrostatic spinning water-oil separating of imidization tunica fibrosa is the preparation of CA-PI tunica fibrosa: traditionalOn the basis of electric spinning equipment, adopt coaxial syringe needle, the DMAc solution of 1-5% (wt) PAA is as core, 5-10% (wt)Carrene and the mixed solution of acetone 2: 1 (V/V) as shell, spinning in high-voltage electrostatic field flies High Rotation SpeedWheel receives CA-PAA nanofiber. By CA-PAA nano fibrous membrane good electrospinning according to 150 DEG C/2h of temperature programming,200/3h, 250 DEG C/1h, the method for 260 DEG C/1h is carried out imidization and is obtained CA-PI nano fibrous membrane; The nanometer fibre obtainingThe universal testing machine (CMT-8500 type) that dimension film adopts Shenzhen newly to think carefully at room temperature carries out test stress one strain.
6. the preparation method of efficient electrostatic spinning water-oil separating tunica fibrosa according to claim 1, described in it is characterized in thatThe synthetic benzoxazine monomer of step (5):
1) by bisphenol A/F, paraformaldehyde and m-benzotrifluoride amine 14.7g respectively, 5.3g and 14.1g, add successively condensation be housedReturn duct, electric blender, N2In the four-hole bottle of wireway, thermometer;
2) heating is until reactant thickness is difficult to stir, and question response thing is cooled to room temperature, adds CHCl to it3200ml entersRow dissolves;
3), with the above-mentioned dissolving of the NaOH solution washing mixed solution completely of mass fraction 2%, treat that solution layering takes off a layer solution.The solution of separating is added to the CHCl of 50ml3；
4) after stirring, add the anhydrous calcium chloride (CaCl of 2g2) dehydration;
5) solution after dehydration is dried, obtains the monomer powders of fluorine-containing benzoxazine.
7. the preparation method of efficient electrostatic spinning water-oil separating tunica fibrosa according to claim 1, described in it is characterized in thatStep (6) BAF-tfa and BAF-tfa/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI,CA-PI nano fibrous membrane;
1) take 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, the fluorine-containing benzoxazine BAF-tfa of 0.1g and 0.4g is mono-Body powder, is respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% according to mass fraction and dissolvesIn butyl acetate (ButylAcetate), obtain dissolving completely and mix the clear solution of homogeneous;
2) by the laboratory sample of CA, PI, CA-PI tunica fibrosa cutting 2 × 2cm width and the length of preparation, and by this fibreDimension film immersion is in the butyl acetate solution that is dissolved with fluorine-containing benzoxazine BAF-tfa;
3) with taking the photograph son, CA, the PI, the CA-PI tunica fibrosa that are immersed in mixed solution are taken out rapidly, first in natural conditionsUnder dry, then put vacuum into and be cured for case; Be cooled to afterwards room temperature, taking-up F-PBZ/CA, F-PBZ/PI,F-PBZ/CA-PI is for subsequent use.
4) take 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, the BAF-tfa monomer powders of 0.1g and 0.4g, according toMass fraction is respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% and is dissolved in butyl acetate(ButylAcetate) in;
5) and to add mass fraction be 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% SiO2NPsIn butyl acetate solution, obtain dissolving completely and mix the clear solution of homogeneous;
6) by the laboratory sample of CA, PI, CA-PI tunica fibrosa cutting 2 × 2cm width and the length of preparation, and by this fibreDimension film immersion is being dissolved with BAF-tfa and SiO2In the butyl acetate liquid of NPs; Finally, will be immersed in mixed solution with tweezersIn tunica fibrosa take out rapidly, first dry under field conditions (factors), then put vacuum drying oven into and be cured 2h, cooling afterwardsTo room temperature, take out F-PBZ/SNP/CA, F-PBZ/SNP/PI, F-PBZ/SNP/CA-PI for subsequent use.
8. the preparation method of efficient electrostatic spinning water-oil separating tunica fibrosa according to claim 1, described in it is characterized in thatStep (7) water-oil separating experiment:
1) measure respectively carrene and the water of 10ml,Water methylene blue staining, oil (carrene) dyes with oil red. By after the oil mixing with water solution left standstill 1min of 200ml,Profit separates. Be dyed to blue water on upper strata, red oil is in lower floor, F-PBZ--1/SNP-4/CA-PI function fibreDimension film is fixed between two glass tubes. Then, the mixed solution of layering is poured in glass tube above, carried out profitSeparate. Red oil permeates F-PBZ-1/SNP-4/CA-PI tunica fibrosa rapidly, flows in beaker below, and blueWater is still stayed in the glass tube on upper strata, and records the time that profit is separated completely, and measure separate before with separate afterThe volume of water.
2) select respectively different oil water mixtures (carrene-water, bromobenzene-water, carbon tetrachloride-water, chloroform-Water and 1,2-dichloroethanes-water) 20ml (1/1 (V/V)), according to 1) carry out water-oil separating experiment.
3) the CA-PAA film of electrospinning different-thickness imidization obtain CA-PI film respectively, at the BAF-tfa through 1wt%And 4wt%SiO2NPs in-situ solidifying obtains different-thickness F-PBZ-1/SNP-4/CA-PI film. And by 1) carry out profitSeparating experiment.
4) select F-PBZ-1/SNP-4/CA-PI film, and by 1) carry out repeatedly water-oil separating.
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