CN107875673A - A kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane - Google Patents
A kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane Download PDFInfo
- Publication number
- CN107875673A CN107875673A CN201610877394.8A CN201610877394A CN107875673A CN 107875673 A CN107875673 A CN 107875673A CN 201610877394 A CN201610877394 A CN 201610877394A CN 107875673 A CN107875673 A CN 107875673A
- Authority
- CN
- China
- Prior art keywords
- cho
- nano fibrous
- paa
- preparation
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
-
- 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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- 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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
-
- 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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention is a kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane, 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 (BA CHO)；BA CHO and BA CHO/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA PI nano fibrous membrane；Water-oil separating is tested.Advantage：By to fiber membrane surface modification, obtaining with biodegradability, cost is cheap, CA PI nano fibrous membranes 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
It is particularly a kind of to be used for weight the present invention relates to a kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane
Power drives a kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane 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, gathered in oneself
Ester, 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, easily produce secondary pollution the shortcomings that.And the film of common super-hydrophobic super-oleophylic
Material, in use, easily polluted by oil, greatly reduce the performance of its reuse.Simultaneously intensity difference this
Maximum obstacle, seriously limits their applications in practice.
The content of the invention
Proposed by the present invention is a kind of superhydrophilic superoleophobic type electrostatic spinning profit point that water-oil separating is driven for gravity
From the preparation method of tunica fibrosa, its purpose is intended to the drawbacks described above for overcoming prior art to have, and uses CA and PAA as raw material,
By high voltage co-axial electrostatic spinning technique using the poly- PAA of HMW as core, CA is shell, and PAA is being carried out by temperature programming
Imidization obtains having that biodegradability, cost are cheap, significantly separate the CA-PI of flux, separative efficiency and mechanical strength
Nano fibrous membrane；By to tunica fibrosa surface modification, obtaining functional fiber film material；It is moreover, this efficient super-hydrophobic
Super oleophylic membrane material has broad application prospects in the leakage of water-oil separating, sewage disposal and deep-sea oil.
The technical solution of the present invention：A kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane, including it is as follows
Processing step：
(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) benzoxazine monomer (BA-CHO) is synthesized；
(6) BA-CHO and BA-CHO/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PI nanometers
Tunica fibrosa；
(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；
B. there is high intensity, tensile strength reaches more than 200MPa, and the stretching compared to conventional CA nano fibrous membranes is strong
6.65MPa is spent, improves more than 30 times；
C. 125 ° only are can only achieve by the Maximum Contact angle of the CA-PI nano fibrous membranes that BA-CHO is modified and oil, not
With super hydrophilic and superoleophobic property；And pass through most contact angle of the modified CA-PI nano fibrous membranes of BA-CHO under water with oil
Up to 151 °, the contact angle of air reclaimed water can reach 0 °, have super hydrophilic and superoleophobic property, available for water-oil separating
Journey.
Brief description of the drawings
Fig. 1 is the process schematic of coaxial electrically spun CA-PI nano fibrous membranes.
Embodiment
A kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane, is comprised the technical steps that：
(1) PAA is synthesized；
Bibenzene tetracarboxylic two is added in the drying four-hole boiling flask that pipe is exported equipped with mechanical agitator, thermometer, nitrogen
2.9422 and 1.0814g (mol ratio 1: 1) is well mixed respectively for acid anhydride (BPDA) and p-phenylenediamine (PDA)；Stirred in strong machinery
Mix down, add 40ml DMAc, after reacting 24h hours at -15 DEG C -5 DEG C, then terminate to react, obtain PAA.
(2) electrospinning PAA nano fibrous membranes and imines turn to polyimides (PI) film：
With 1-5% (wt) PAA DMAc solution, the spinning in the high-voltage electrostatic field that voltage is 30kV (+20, -10kV), note
The reception distance of emitter needle point to flywheel is 10-15cm, and the rotating speed of flywheel turns/min for 1000-2000, and the speed of electrospinning is
0.5-1ml/h, polyamic acid (PAA) nano fibrous membrane is spun to, as shown in Figure 1.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/30mim method carries out Asia in tube furnace
Amination obtains PI films；The universal testing machine (CMT-8500 types) newly thought carefully with Shenzhen afterwards strains to the stress one of PI films
Tested at room temperature, test 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, is spun to
CA nano fibrous membranes, the universal material that electric spinning equipment is newly thought carefully with the device of electrospinning PAA films, obtained nano fibrous membrane Shenzhen
Testing machine (CMT-8500 types) 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 as core, 5-10% (wt) dichloromethane and the mixed solution conduct of acetone 2: 1 (V/V)
Shell, the spinning in high-voltage electrostatic field, rotatably flywheel carries out receiving CA-PAA nanofibers at a high speed.The good CA-PAA of electrospinning is received
Rice tunica fibrosa carries out imidization and obtains CA- according to 150 DEG C of temperature programming/2h, 200/3h, 250 DEG C/1h, 260 DEG C/1h method
PI nano fibrous membranes；The universal testing machine (CMT-8500 types) that obtained nano fibrous membrane is newly thought carefully using Shenzhen is in room temperature
Lower progress test stress-strain.
(5) benzoxazine monomer is synthesized
1) paraformaldehyde is dissolved in 6ml toluene, is added in there-necked flask and reduces its temperature to 5 DEG C, 1.86g aniline
Less than 5 DEG C are cooled to 2ml toluene, rapid stirring, and 30min is stirred, it is added in there-necked flask, 2.44g para hydroxybenzene first
Aldehyde is dissolved in 6ml toluene, is added in there-necked flask, is stirred vigorously.Then temperature is warmed to room temperature, first stirs 1h, then slowly
95 DEG C are heated to, stirs 5h.
2) question response thing is cooled to room temperature, is evaporated under reduced pressure and removes solvent, and CHCl is added to it3200ml is dissolved；With
The 0.5mol/L complete mixed solution of the above-mentioned dissolving of the NaOH aqueous solution and water washing, treat that a layer solution is removed in solution layering.It will divide
Separate out the CHCl that the solution come adds 50ml3；The uniformly rear anhydrous calcium chloride (CaCl for adding 2g to be mixed2) dehydration；It will be dehydrated
Solution afterwards is dried, and obtains the monomer powders of benzoxazine.
(6) BA-CHO and BA-CHO/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PI nanometers
Tunica fibrosa；
1) 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, 0.1g and 0.4g benzoxazine BA-CHO monomers are weighed
Powder, it is respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% to be dissolved in acetone according to mass fraction
In, obtain dissolving completely and mix homogeneous clear solution；
2) CA, PI, CA-PI tunica fibrosa of preparation is cut into 2 × 2cm width and the laboratory sample of length, and by the fiber
Film immersion is in the acetone soln dissolved with benzoxazine BA-CHO；
3) CA, PI, CA-PI tunica fibrosa being immersed in mixed solution taken out rapidly with taking the photograph son, first under field conditions (factors)
Dry, then put vacuum into and solidified for case；Room temperature is cooled to afterwards, takes out PBZ-CHO/SNP/CA, PBZ-CHO/SNP/
PI, PBZ-CHO/SNP/CA-PI are standby.
4) 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, 0.1g and 0.4g BA-CHO monomer powders are weighed, are pressed
According to mass fraction be respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% dissolving in acetone；
5) and mass fraction is added as 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% SiO2
NPs obtains dissolving completely and mixes homogeneous clear solution into acetone soln；
6) CA, PI, CA-PI tunica fibrosa of preparation is cut into 2 × 2cm width and the laboratory sample of length, and by the fiber
Film immersion is dissolved with BA-CHO and SiO2In NPs acetone soln；Finally, the fiber that will be immersed in tweezers in mixed solution
Film takes out rapidly, first dries under field conditions (factors), then puts vacuum drying oven into and carry out solidification 2h, be cooled to room temperature afterwards, takes out
PBZ-CHO/SNP/CA, PBZ-CHO/SNP/PI, PBZ-CHO/SNP/CA-PI are standby.
(7) contact angle experiments,
CA, PI for being modified using contact angle experiments instrument to different concentration benzoxazines and Nano particles of silicon dioxide,
CA-PI nano fibrous membranes, PBZ-CHO/CA, PBZ-CHO/CA and PBZ-CHO/CA-PI and PBZ-CHO/SNP/CA, PBZ-
The hydrophobic performance of sample obtained by the above-mentioned each concentration of CHO/SNP/PI, PBZ-CHO/SNP/CA-PI composite cellulosic membrane and parent
The static contact angle of oiliness energy is studied.
(8) water-oil separating is tested：
10ml dichloromethane and water, water methylene blue staining are measured respectively, and oily (n-hexane) is dyed with oil red.Will
After 20ml oil mixing with water solution left standstill 1min, profit separates.The water of blueness is dyed in lower floor, red oil is upper
Layer, PBZ-CHO-1/SNP-4/CA-PI functional fibre films are fixed between two glass tubes.Then, it is the mixing of layering is molten
Liquid is poured into glass tube above, carries out water-oil separating.The water of blueness rapidly permeates PBZ-CHO-1/SNP-4/CA-PI fibers
Film, flow in following beaker, and red oil is still remained in the glass tube on upper strata, and record profit it is completely isolated when
Between, and the volume before measurement separation with water after separation.
Of the invention is exactly mainly that coaxial electrically spun obtains coaxial CA-PI nano fibrous membranes, and that does before uses BA-CHO and SiO2
The CA, stress 6.65MPa that NPs is modified；And we when do to electrospinning into coaxial CA-PI nano fibrous membranes, just look like
A steel wire, the BA-CHO and SiO after high temperature imidization are added inside the poor CA of mechanical property2What NPs was modified
CA-PI films, improve its strain and be more than 200MPa.In the application of actual water-oil separating, access times can be greatly improved.Overcome
Existing electrospinning film poor mechanical property, easily pollution in actual water-oil separating application, it is not durable in use the shortcomings that.Add existing
There is the usable number of water-oil separationg film, saved financial cost.
Claims (8)
- A kind of 1. preparation method of superhydrophilic superoleophobic type nano fibrous membrane, 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) benzoxazine monomer (BA-CHO) is synthesized；(6) BA-CHO and BA-CHO/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PI nanofibers Film；(7) water-oil separating is tested.
- A kind of 2. preparation method of superhydrophilic superoleophobic type nano fibrous membrane according to claim 1, it is characterized in that described The step of (1) synthesizing polyamides it is sour (PAA)；The drying four-hole boiling flask into pipe is being exported equipped with mechanical agitator, thermometer, nitrogen Middle addition bibenzene tetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) 2.9422 and 1.0814g of difference (mol ratio 1: 1), mixing Uniformly；Under strong mechanical agitation, DMAc40ml is added, after reacting 24h hours at -15 DEG C -5 DEG C, then terminates to react, Obtain polyamic acid.
- A kind of 3. preparation method of superhydrophilic superoleophobic type nano fibrous membrane according to claim 1, it is characterized in that described The step of (2) PAA nano fibrous membranes preparation and imines turn to polyimides (PI) film：DMAc with 1-5% (wt) PAA is molten Liquid, the spinning in the high-voltage electrostatic field that voltage is 30kV (+20, -10kV), the reception distance of syringe needle point to flywheel is 10- 15cm, the rotating speed of flywheel turn/min for 1000-2000, and the speed of electrospinning is 0.5-1ml/h, is spun to PAA nano fibrous membranes.Will The good PAA nano fibrous membranes of electrospinning are according to 150 DEG C/1h of temperature programming, 200 DEG C/1h, 250 DEG C/1h, 300 DEG C/1h, 350 DEG C/ 30mim method carries out imidization in tube furnace and obtains PI films；Universal testing machine (the CMT- newly thought carefully with Shenzhen afterwards 8500 types) stress-strains of PI films is tested at room temperature, test its stress-strain.
- A kind of 4. preparation method of superhydrophilic superoleophobic type nano fibrous membrane according to claim 1, it is characterized in that described The step of (3) CA nano fibrous membranes preparation：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, is spun to CA nano fibrous membranes, the universal material that electric spinning equipment is newly thought carefully with the device of electrospinning PAA films, obtained nano fibrous membrane Shenzhen Testing machine (CMT-8500 types) carries 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) and imidization The preparation method of efficient electrostatic spinning water-oil separating tunica fibrosa is the preparation of CA-PI tunica fibrosas：It is in traditional electric spinning equipment On the basis of use coaxial syringe needle, 1-5% (wt) PAA DMAc solution is as core, 5-10% (wt) dichloromethane and third The mixed solution of ketone 2: 1 (V/V) is as shell, the spinning in high-voltage electrostatic field, at a high speed rotatably flywheel carry out receive CA-PAA receive Rice fiber.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 carries out imidization and obtains CA-PI nano fibrous membranes；Obtained nano fibrous membrane uses the omnipotent material that Shenzhen is newly thought carefully Expect that testing machine (CMT-8500 types) carries out test stress-strain at room temperature.
- A kind of 6. preparation method of superhydrophilic superoleophobic type nano fibrous membrane according to claim 1, it is characterized in that described The step of (5) synthesis benzoxazine monomer：1) paraformaldehyde is dissolved in 6ml toluene, is added in there-necked flask and reduces its temperature to 5 DEG C, 1.86g aniline and 2ml toluene is cooled to 5 DEG C once, rapid stirring, and stirs 30min, is added in there-necked flask, 2.44g parahydroxyben-zaldehydes It is dissolved in 6ml toluene, is added in there-necked flask, is stirred vigorously.Then temperature is warmed to room temperature, first stirs 1h, then slowly added Heat stirs 5h to 95 DEG C.2) question response thing is cooled to room temperature, is evaporated under reduced pressure and removes solvent, and CHCl is added to it3200ml is dissolved；3) the 0.5mol/L NaOH aqueous solution and the complete mixed solution of the above-mentioned dissolving of water washing is used, it is molten to treat that layer is removed in solution layering Liquid.The solution separated is added to 50ml CHCl3；4) the uniformly rear anhydrous calcium chloride (CaCl for adding 2g to be mixed2) dehydration；5) solution after dehydration is dried, obtains the monomer powders of benzoxazine.
- A kind of 7. preparation method of superhydrophilic superoleophobic type nano fibrous membrane according to claim 1, it is characterized in that described The step of (6) BA-CHO and BA-CHO/ Nano particles of silicon dioxide (SiO2NPs) in-situ solidifying CA, PI, CA-PI Nanowires Tie up film；1) 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, 0.1g and 0.4g fluorine-containing benzoxazine BA-CHO monomers are weighed Powder, it is respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% to be dissolved in acetone according to mass fraction In, obtain dissolving completely and mix homogeneous clear solution；2) CA, PI, CA-PI tunica fibrosa of preparation are cut into 2 × 2cm width and the laboratory sample of length, and the tunica fibrosa is soaked Stain is in the acetone soln dissolved with benzoxazine BA-CHO；3) CA, PI, CA-PI tunica fibrosa being immersed in mixed solution taken out rapidly with taking the photograph son, first dried under field conditions (factors), Then vacuum is put into for case to be solidified；Room temperature is cooled to afterwards, takes out PBZ-CHO/CA, PBZ-CHO/PI, PBZ-CHO/CA- PI is standby.4) 0.001g, 0.002g, 0.005g, 0.01g, 0.05g, 0.1g and 0.4g BA-CHO monomer powders are weighed, according to matter Amount fraction be respectively 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% dissolving in acetone；5) and mass fraction is added as 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 4.0% hydrophily SiO2NPs obtains dissolving completely and mixes homogeneous clear solution into acetone soln；6) CA, PI, CA-PI tunica fibrosa of preparation are cut into 2 × 2cm width and the laboratory sample of length, and the tunica fibrosa is soaked Stain is dissolved with BA-CHO and SiO2In NPs acetone soln；Finally, it is with tweezers that the tunica fibrosa being immersed in mixed solution is rapid Take out, first dry under field conditions (factors), then put vacuum drying oven into and carry out solidification 2h, be cooled to room temperature afterwards, take out PBZ- CHO/SNP/CA, PBZ-CHO/SNP/PI, PBZ-CHO/SNP/CA-PI are standby.
- A kind of 8. preparation method of superhydrophilic superoleophobic type nano fibrous membrane according to claim 1, it is characterized in that described The step of (7) water-oil separating test：10ml dichloromethane and water, water methylene blue staining are measured respectively, and oily (n-hexane) is dyed with oil red.By 20ml's After oil mixing with water solution left standstill 1min, profit separates.The water of blueness is dyed in lower floor, red oil is in upper strata, PBZ- CHO-1/SNP-4/CA-PI functional fibre films are fixed between two glass tubes.Then, the mixed solution of layering is poured into In the glass tube in face, water-oil separating is carried out.The water of blueness rapidly permeates PBZ-CHO-1/SNP-4/CA-PI tunica fibrosas, flows to In following beaker, and red oil is still remained in the glass tube on upper strata, and records the profit completely isolated time, and The preceding volume with water after separation of measurement separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610877394.8A CN107875673A (en) | 2016-09-29 | 2016-09-29 | A kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610877394.8A CN107875673A (en) | 2016-09-29 | 2016-09-29 | A kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107875673A true CN107875673A (en) | 2018-04-06 |
Family
ID=61769602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610877394.8A Pending CN107875673A (en) | 2016-09-29 | 2016-09-29 | A kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107875673A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794752A (en) * | 2018-04-26 | 2018-11-13 | 中国科学院兰州化学物理研究所 | A kind of Thermocurable polyimide and its application |
| CN110112405A (en) * | 2019-05-29 | 2019-08-09 | 哈尔滨理工大学 | A kind of core-shell structure silicon/carbon fiber flexible combination electrode material and the preparation method and application thereof |
| CN110368718A (en) * | 2019-06-28 | 2019-10-25 | 天津大学 | A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof |
| CN112933984A (en) * | 2021-01-29 | 2021-06-11 | 三明学院 | GYSNs (gysan) -filled polyurethane hybrid film and preparation method thereof |
| CN112933979A (en) * | 2021-01-29 | 2021-06-11 | 三明学院 | MYNs filled polyethylene glycol composite membrane and preparation method thereof |
| CN115722209A (en) * | 2022-09-27 | 2023-03-03 | 东华大学 | Polyoxymethylene microfiber oil-water separation material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603637A (en) * | 2016-01-19 | 2016-05-25 | 南京林业大学 | Efficient electrostatic spinning oil-water separation fiber membrane |
-
2016
- 2016-09-29 CN CN201610877394.8A patent/CN107875673A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603637A (en) * | 2016-01-19 | 2016-05-25 | 南京林业大学 | Efficient electrostatic spinning oil-water separation fiber membrane |
Non-Patent Citations (1)
| Title |
|---|
| 杨姗: "超亲水SiO2纳米纤维多孔膜的可控制备及其微乳液分离应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794752A (en) * | 2018-04-26 | 2018-11-13 | 中国科学院兰州化学物理研究所 | A kind of Thermocurable polyimide and its application |
| CN110112405A (en) * | 2019-05-29 | 2019-08-09 | 哈尔滨理工大学 | A kind of core-shell structure silicon/carbon fiber flexible combination electrode material and the preparation method and application thereof |
| CN110112405B (en) * | 2019-05-29 | 2021-05-18 | 哈尔滨理工大学 | Core-shell structure silicon/carbon fiber flexible composite electrode material and preparation method and application thereof |
| CN110368718A (en) * | 2019-06-28 | 2019-10-25 | 天津大学 | A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof |
| CN112933984A (en) * | 2021-01-29 | 2021-06-11 | 三明学院 | GYSNs (gysan) -filled polyurethane hybrid film and preparation method thereof |
| CN112933979A (en) * | 2021-01-29 | 2021-06-11 | 三明学院 | MYNs filled polyethylene glycol composite membrane and preparation method thereof |
| CN112933979B (en) * | 2021-01-29 | 2022-05-10 | 三明学院 | MYNs filled polyethylene glycol composite membrane and preparation method thereof |
| CN115722209A (en) * | 2022-09-27 | 2023-03-03 | 东华大学 | Polyoxymethylene microfiber oil-water separation material and preparation method thereof |
| CN115722209B (en) * | 2022-09-27 | 2024-04-12 | 东华大学 | Polyoxymethylene microfiber oil-water separation material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107875673A (en) | A kind of preparation method of superhydrophilic superoleophobic type nano fibrous membrane | |
| CN104988662B (en) | The preparation method of nano fibrous membrane | |
| CN105603637A (en) | Efficient electrostatic spinning oil-water separation fiber membrane | |
| Cheng et al. | Cellulose nanocrystal coated cotton fabric with superhydrophobicity for efficient oil/water separation | |
| CN109731479B (en) | Preparation method of super-hydrophobic nanofiber membrane and super-hydrophobic nanofiber membrane | |
| CN100586537C (en) | Reinforced microporous filter membrane and method and device for preparing the same | |
| CN104342850B (en) | polyimide film containing nanocrystal cellulose and preparation method thereof | |
| CN104562292B (en) | Preparation method of porous micro-nano PET fibers | |
| CN105597574B (en) | A kind of preparation method of compound forward osmosis membrane | |
| CN101748604A (en) | Method for preparing lyophobic oil-absorption fiber surfaces | |
| CN104209018B (en) | A kind of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane and preparation method thereof | |
| CN104452287B (en) | Height ventilative super-hydrophobic polyvinyl alcohol nano non-weaving cloth, its preparation method and application | |
| CN107142610B (en) | A kind of high-performance stereocomplex PLA Electrospun nano-fibers film and preparation method thereof | |
| CN110055807A (en) | A kind of p-aramid fiber and graphene oxide/graphene extrusion coating paper preparation method | |
| Fan et al. | Electro-blown spun PS/PAN fibrous membrane for highly efficient oil/water separation | |
| Kong et al. | Three-dimensional and flexible carbon nanofiber mat by one-step electrospinning for efficient oil/water separation | |
| CN103387687A (en) | Preparation method of chitosan nanometer fiber resin composite film material | |
| CN107151862A (en) | A kind of preparation method of high-efficiency nano fibre water-oil separationg film | |
| CN112796001A (en) | Anti-wrinkle antibacterial polyester staple fiber | |
| CN105734696A (en) | Preparation method for polystyrene-polyvinylidene fluoride coaxial electrospun fiber | |
| CN107321192A (en) | A kind of preparation method of the water-oil separationg film of high flux pH responses | |
| CN108939952A (en) | A kind of water-oil separating PMIA super-hydrophobic nano tunica fibrosa and preparation method | |
| CN101717507A (en) | Static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber | |
| CN108771977A (en) | A kind of preparation method of the super-hydrophobic super-oleophylic nano fibrous membrane based on layer-by-layer for oil water mixture separation | |
| CN107326652A (en) | A kind of preparation method of the nanofiber water-oil separationg film of pH responses |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180406 |