CN107447496B - A kind of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, preparation method and applications - Google Patents
A kind of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, preparation method and applications Download PDFInfo
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- CN107447496B CN107447496B CN201710641481.8A CN201710641481A CN107447496B CN 107447496 B CN107447496 B CN 107447496B CN 201710641481 A CN201710641481 A CN 201710641481A CN 107447496 B CN107447496 B CN 107447496B
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229960004643 cupric oxide Drugs 0.000 title claims abstract description 67
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 238000009987 spinning Methods 0.000 claims abstract description 25
- 239000005751 Copper oxide Substances 0.000 claims abstract description 24
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 18
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 241000530268 Lycaena heteronea Species 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 26
- 239000003921 oil Substances 0.000 description 24
- 235000019198 oils Nutrition 0.000 description 19
- 239000000463 material Substances 0.000 description 11
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- IILUTRCPUABLDZ-UHFFFAOYSA-N acetyl acetate;copper Chemical compound [Cu].CC(=O)OC(C)=O IILUTRCPUABLDZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 4
- 239000004006 olive oil Substances 0.000 description 4
- 235000008390 olive oil Nutrition 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 240000007472 Leucaena leucocephala Species 0.000 description 3
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000008157 edible vegetable oil Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000010729 system oil Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
- D06M11/42—Oxides or hydroxides of copper, silver or gold
-
- 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
-
- 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
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
-
- 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
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
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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
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/22—Polymers or copolymers of halogenated mono-olefins
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
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- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece films, preparation method and applications, and this method comprises the following steps: step 1, the preparation of spinning solution；The spinning solution is prepared organic/inorganic hybrid nano tunica fibrosa by electrostatic spinning by step 2；The hybrid nano fibrous membrane is baked, cools down to obtain the nano fibrous membrane that fiber surface has copper oxide seed by step 3；The nano fibrous membrane that fiber surface has copper oxide seed is put into copper oxide growth-promoting media by step 4, it is sealed later, 50-60 DEG C reaction after, be cooled to room temperature to get.This method growth temperature is low, strong operability, and the super hydrophilic film of gained shows excellent flexible nature, has established solid foundation for actual application.
Description
Technical field
The invention belongs to functional nanomaterials technical fields, and in particular to a kind of super hydrophilic nucleocapsid Kynoar hexafluoro
Propylene/cupric oxide nano piece film, preparation method and its usage.
Background technique
Since the oil water mixture that Oil spills problem and industrial and agricultural production generate increasingly influences people's lives,
Therefore water-oil separating problem has become the hot fields of whole world researcher concern.Traditional process such as air is floating
Select method, gravitational separation process, oil absorption material, coagulation etc. due to low separative efficiency, high energy consumption and separation equipment of complexity etc.
Disadvantage brings many limitations to practical application, very poor (with reference to text especially for the lesser oil hydrosol separating effect of partial size
Offer 1:Yang H C, Liao K J, Huang H, et al.Mussel-inspired modification of a polymer
membrane for ultra-high water permeability and oil-in-water emulsion
separation[J].Journal of Materials Chemistry A,2014,2(26):10225-10230.)。
Membrane separation technique equipment is simple, low energy consumption, applied widely, separative efficiency is high, has in terms of oil hydrosol separation
Wide application prospect.However, the seperation film with superhydrophobic characteristic can form the interface of one layer of water among oil and film,
It hinders oil to penetrate seperation film, separative efficiency is caused to decline.And due to the low surface energy in super-hydrophobic film surface, it be easy to cause film
Pollution problem makes energy consumption increase and flux depression.And super hydrophilic membrane material shows underwater superoleophobic characteristic, can be effectively improved
Membrane pollution problem has broad application prospects (bibliography 2:Shi H, He Y, Pan Y, et in oil hydrosol separation field
al.A modified mussel-inspired method to fabricate TiO2decorated
superhydrophilic PVDF membrane for oil/water separation[J].Journal of
Membrane Science,2016,506:60-70.)。
However, inorganic super hydrophilic membrane material before is typically prepared process complexity, very high calcination temperature (one is generally required
As be greater than 400 degree) or the higher growth temperature of needs (more than 100 degree).These shortcomings not only make in preparation process
Requirement height, energy consumption cost to equipment increase, and there are security risks in preparation process.
In addition, often flexibility is poor for inorganic separating film, breakage is easily snapped off in use process.Not only imitate UF membrane
Rate decline, and the service life of seperation film is greatly shortened.
" 106731012 A of CN " disclose " it is a kind of it is super infiltration titanium dioxide nano-rod perforated membrane preparation and its in lotion
Application in separation " needs 500-600 DEG C of calcination temperature and 120-150 DEG C of growth temperature in preparation process.500-
Requirement of 600 DEG C of the calcination temperature to equipment is very high, and energy consumption and cost are all bigger in use process, and there are security risks.
Growth temperature is 120-150 DEG C, limits the popularization of actual large-scale production.
Summary of the invention
The present invention is directed at least solve one of the technical problems existing in the prior art.For this purpose, the present invention provides a kind of surpass
Hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, preparation method and its usage, it is therefore an objective under cryogenic
Prepare the nano fibrous membrane of super hydrophilic super flexible nature.
To achieve the goals above, the technical scheme adopted by the invention is as follows:
A kind of preparation method of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, including walk as follows
It is rapid:
Salicylaldoxime is dissolved in binary organic solvent by step 1, and being added account for total solution mass fraction later is 10-
20% Kynoar-hexafluoropropene (PVDF-HFP), it is agitated to obtain spinning solution, Salicylaldoxime and Kynoar-
The mass ratio of hexafluoropropene is 1:2-6；
The spinning solution is prepared organic/inorganic hybrid nano tunica fibrosa by electrostatic spinning by step 2；
The hybrid nano fibrous membrane is baked, cools down to obtain fiber surface and have copper oxide by step 3
The nano fibrous membrane of seed；
The nano fibrous membrane that fiber surface has copper oxide seed is put into copper oxide growth-promoting media by step 4, after through close
Envelope, 50-60 DEG C reaction after, be cooled to room temperature to get.
The Salicylaldoxime and Kynoar-hexafluoropropene mass ratio are 1:2-3.Using this proportion so that anhydrous
Acetic acid copper content is higher, and in this way during baking, fiber surface has more copper oxide seeds and generates.In hydrothermal growth
When cupric oxide nano piece, more growing points are had.Also it is easier to obtain the fiber that fiber surface covers with cupric oxide nano piece
Film.
The device for spinning that the electrostatic spinning uses includes receiver board, solution tank, dials and for driving on solution tank
The driving motor of dials rotation, the technological parameter of electrostatic spinning include: to apply voltage 20-30kV, and receiving distance is 15-40cm,
Dials revolving speed 10-15r/min.
The temperature baked in the step 3 is 100-120 DEG C, baking time 12-24h.When reasonable temperature and baking
Between, more conducively fiber surface Salicylaldoxime chemically reacts, and generates copper oxide, has copper oxide seed convenient for fiber surface
The generation of nano fibrous membrane.
The preparation method of the copper oxide growth-promoting media is that Salicylaldoxime is dissolved in water, and ammonium hydroxide is added dropwise later to precipitating whole
It dissolves up to transparent navy blue copper ammon solution.It is added dropwise during ammonium hydroxide, obtains Cu (OH) first2Precipitating continues that ammonium hydroxide is added dropwise, directly
To precipitating all dissolutions, transparent navy blue copper ammon solution, as copper oxide growth-promoting media are just obtained.Salicylaldoxime is dissolved in water-soluble
In liquid, ammonium hydroxide is then added dropwise into acetic anhydride copper liquor.The requirement of this growth-promoting media preparing materials is low, configuration process is succinct, can
Control property is good, meets the needs of practical application.
The binary organic solvent is that n,N-Dimethylformamide (DMF) and acetone (Acetone) is formed.
The mass ratio of the n,N-Dimethylformamide and acetone is 1:1.Under this proportion, be conducive to the smooth of spinning process
It carries out, obtains the nano fibrous membrane that surface is smooth, diameter is evenly distributed.
The present invention also provides a kind of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, use is above-mentioned
Preparation method is made.
The present invention also provides a kind of purposes of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film,
For improving oil and water separation capability.
Beneficial effects of the present invention:
1, high-temperature calcination is not needed, low for equipment requirements, common baking oven can be met the requirements.
2, growth temperature is low, strong operability, needs relative to more than 100 DEG C hydro-thermal reactions using reaction kettle, increase at
This was unfavorable for for the problem of promoting, and growth temperature only needs 50-60 DEG C, and common glass container can meet condition, shows
Fabulous actual application prospect.
3, super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film of the invention, core part are polymer,
Shell parts are inorganic matter, and this unique structure had not only remained the flexible nature of polymer, but also embody the function spy of inorganic matter
Property.Excellent flexible nature is shown, has established solid foundation for actual application.
4, high to oil hydrosol separative efficiency, high separative efficiency can be reached under different conditions, to olive oil, eaten
The separative efficiency of oil and lubricating oil is more than 99.8%.The oil hydrosol of different emulsion temperatures and different salt ionic concentrations is separated,
Show the wide scope of application.
Detailed description of the invention
This specification includes the following drawings, and shown content is respectively:
Fig. 1 is device for spinning structural schematic diagram；
Fig. 2 is hybrid nano fibrous membrane FE-SEM figure；
Fig. 3 is that fiber surface has the organic/inorganic nano tunica fibrosa FE-SEM of copper oxide seed to scheme；
Fig. 4 is super hydrophilic nucleocapsid PVDF-HFP/ cupric oxide nano piece film FE-SEM figure；
Fig. 5 is super hydrophilic nucleocapsid PVDF-HFP/ cupric oxide nano piece film FE-SEM enlarged drawing；
Fig. 6 is super hydrophilic nucleocapsid PVDF-HFP/ cupric oxide nano piece film FE-SEM sectional view；
Fig. 7 is super hydrophilic nucleocapsid PVDF-HFP/ cupric oxide nano piece film FE-SEM enlarged section；
Fig. 8 is super hydrophilic nucleocapsid PVDF-HFP/ cupric oxide nano piece nano fibrous membrane flexible nature display diagram；
Fig. 9 is that super hydrophilic nucleocapsid PVDF-HFP/ cupric oxide nano piece nano fibrous membrane carries out super hydrophilic test in air
Water static contact angle figure；
Figure 10 is that super hydrophilic nucleocapsid PVDF-HFP/ cupric oxide nano piece nano fibrous membrane is oily in superoleophobic test under water
Underwater contact angle figure；
Figure 11 is optics picture before oil hydrosol separates；
Figure 12 is that optics picture after water-oil separating is carried out using the present invention.
In the figure, it is marked as
1, receiver board, 2, high-voltage DC power supply, 3, dials, 4, solution tank.
Specific embodiment
Below against attached drawing, by the description of the embodiment, making to a specific embodiment of the invention further details of
Explanation, it is therefore an objective to those skilled in the art be helped to have more complete, accurate and deep reason to design of the invention, technical solution
Solution, and facilitate its implementation.
Embodiment 1
A kind of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, is obtained as follows:
Step 1 weighs 1.8 grams of Salicylaldoximes, and 15 grams of DMF, 15 grams of Acetone are in 100ml vial, at 60 DEG C
Continuously stir 1h；Under room temperature, 3.6 grams of PVDF-HFP are weighed in acetic anhydride copper solution, 4h is continuously stirred at room temperature, obtains
To blue-tinted transparent spinning solution.
Step 2 is poured into spinning solution in the solution tank of device for spinning (Fig. 1).Adjust electrostatic spinning process parameter are as follows:
Spinning voltage 25kV receives distance 25cm.Dials rotation speed is 12r/min.Obtain hybrid nano fibrous membrane.
From the FE-SEM of Fig. 2 it is found that fiber surface is smooth, fibre diameter is more uniform, and fibre diameter is 198 ± 24nm.
Organic/inorganic nano tunica fibrosa is put into baking oven by step 3, and temperature is 120 DEG C, time 18h.Naturally it drops
Temperature obtains the organic/inorganic nano tunica fibrosa that fiber surface has copper oxide seed.By the FE-SEM of Fig. 3 it is found that fibre diameter becomes
Carefully (161 ± 21nm), fibre diameter is uniform.
Fiber surface is had the organic/inorganic nano tunica fibrosa of copper oxide seed to be put into and fills the glass of growth-promoting media by step 4
In glass bottle.Vial is moved into baking oven after obturaging, temperature is 50 DEG C, time 15h.It is naturally cooling to room temperature, obtains super parent
Water nucleocapsid PVDF-HFP/ cupric oxide nano piece nano fibrous membrane.If the FE-SEM of Fig. 4 is it is found that nanometer sheet is uniformly covered on
The surface PVDF-HFP.By Fig. 6 and Fig. 7 cross-section diagram it is found that core part is PVDF-HFP, shell parts are cupric oxide nano piece.And
Every fiber surface has the growth of copper oxide nanometer sheet.Since core part is polymer, shell parts are inorganic matter, this unique
Structure had not only remained the flexible nature of polymer, but also embodied the functional characteristic of inorganic matter, showed excellent flexible nature (such as
Shown in Fig. 8).
By Cassie model it is found that water wetted material surface is more coarse, the hydrophily of material is stronger.Cupric oxide nano piece is mixed and disorderly
Be grown in the surface PVDF-HFP, show high degree of roughness.Therefore, the nucleocapsid PVDF-HFP/ cupric oxide nano obtained
Piece nano fibrous membrane shows super hydrophilic characteristic, and the static contact angle of water is 0 degree (as shown in Figure 9) in air.With super hydrophilic
The nano fibrous membrane of characteristic shows underwater superoleophobic characteristic, and oily underwater contact angle is 152.9 DEG C (as shown in Figure 10).
Water-oil separating experiment
Oily phase (olive oil, edible oil and lubricating oil) is mixed with deionized water by weight 1:100.Prepared grease
Stir 2 hours under mixed solution elder generation room temperature strongly, then ultrasound 2h at 40 DEG C, obtains water system oil hydrosol (as shown in figure 11).
Oil refers to that content oily in the filtrate after separating compares the mass percent that the content of the preceding oil of separation reduces with water separative efficiency.Separation
Lotion becomes transparent clarification (as shown in figure 12) afterwards, and the separative efficiency of three kinds of oily phases is above 99.8%.And 5 DEG C, 25 DEG C, 40
DEG C solution and 3%, 10%NaCl solution under, separative efficiency shows wide actual application prospect still above 99.8%.
Embodiment 2
A kind of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, is obtained as follows:
Step 1 weighs 1.2 grams of Salicylaldoximes, and 15 grams of DMF, 15 grams of Acetone are in 100ml vial, at 60 DEG C
Continuously stir 1h；Under room temperature, 3.6 grams of PVDF-HFP are weighed in acetic anhydride copper solution, 4h is continuously stirred at room temperature, obtains
To blue-tinted transparent spinning solution.
Step 2 pours into spinning solution in the solution tank of device for spinning.Adjust electrostatic spinning process parameter are as follows: spinning electricity
25kV is pressed, distance 25cm is received.Dials rotation speed is 12r/min.Obtain hybrid nano fibrous membrane.
Organic/inorganic nano tunica fibrosa is put into baking oven by step 3, and temperature is 110 DEG C, time 20h.Naturally it drops
Temperature obtains the organic/inorganic nano tunica fibrosa that fiber surface has copper oxide seed.
Fiber surface is had the organic/inorganic nano tunica fibrosa of copper oxide seed to be put into and fills the glass of growth-promoting media by step 4
In glass bottle.Vial is moved into baking oven after obturaging, temperature is 55 DEG C, time 10h.It is naturally cooling to room temperature, obtains super parent
Water nucleocapsid PVDF-HFP/ cupric oxide nano piece nano fibrous membrane.
By Cassie model it is found that water wetted material surface is more coarse, the hydrophily of material is stronger.Cupric oxide nano piece is mixed and disorderly
Be grown in the surface PVDF-HFP, show high degree of roughness.Therefore, the nucleocapsid PVDF-HFP/ cupric oxide nano obtained
Piece nano fibrous membrane shows super hydrophilic characteristic, and the static contact angle of water is 0 DEG C in air.Nanowire with super hydrophilic characteristic
Dimension film shows underwater superoleophobic characteristic, and oily underwater contact angle is 154.7 DEG C (although acetic anhydride copper content subtracts in spinning solution
It is small, but the increased hydrothermal growth time shows preferably so that more cupric oxide nano pieces are grown in the surface PVDF-HFP
Underwater fuel shedding quality).
Water-oil separating experiment
Oily phase (olive oil, edible oil and lubricating oil) is mixed with deionized water by weight 1:100.Prepared grease
Stir 2 hours under mixed solution elder generation room temperature strongly, then ultrasound 2h at 40 DEG C, obtains water system oil hydrosol.Oil separates effect with water
Rate refers to content oily in the filtrate after separation compared to the mass percent that the content of oil before separation reduces.The separation effect of three kinds of oily phases
Rate is above 99.8%.And 5 DEG C, 25 DEG C, under 40 DEG C of solution and 3%, 10%NaCl solution, separative efficiency still above
99.8%, show wide actual application prospect.
Embodiment 3
A kind of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, is obtained as follows:
Step 1 weighs 0.6 gram of Salicylaldoxime, and 15 grams of DMF, 15 grams of Acetone are in 100ml vial, at 60 DEG C
Continuously stir 1h；Under room temperature, 3.6 grams of PVDF-HFP are weighed in acetic anhydride copper solution, 4h is continuously stirred at room temperature, obtains
To blue-tinted transparent spinning solution.
Step 2 pours into spinning solution in the solution tank of device for spinning.Adjust electrostatic spinning process parameter are as follows: spinning electricity
25kV is pressed, distance 25cm is received.Dials rotation speed is 12r/min.Obtain hybrid nano fibrous membrane.
Organic/inorganic nano tunica fibrosa is put into baking oven by step 3, and temperature is 120 DEG C, and the time is for 24 hours.Naturally it drops
Temperature obtains the organic/inorganic nano tunica fibrosa that fiber surface has copper oxide seed.
Fiber surface is had the organic/inorganic nano tunica fibrosa C of copper oxide seed to be put into and fills the glass of growth-promoting media by step 4
In glass bottle.Vial is moved into baking oven after obturaging, temperature is 50 DEG C, time 15h.It is naturally cooling to room temperature, obtains super parent
Water nucleocapsid PVDF-HFP/ cupric oxide nano piece nano fibrous membrane.
By Cassie model it is found that water wetted material surface is more coarse, the hydrophily of material is stronger.Cupric oxide nano piece is mixed and disorderly
Be grown in the surface PVDF-HFP, show high degree of roughness.Therefore, the nucleocapsid PVDF-HFP/ cupric oxide nano obtained
Piece nano fibrous membrane shows super hydrophilic characteristic, and the static contact angle of water is 0 DEG C in air.Nanowire with super hydrophilic characteristic
Dimension film shows underwater superoleophobic characteristic, oily underwater contact angle be 151.6 DEG C (although in spinning solution acetic anhydride copper content into
One step reduces, but the increased hydrothermal growth time, so that more cupric oxide nano pieces are grown in the surface PVDF-HFP, still table
Reveal preferable underwater fuel shedding quality).
Water-oil separating experiment
Oily phase (olive oil, edible oil and lubricating oil) is mixed with deionized water by weight 1:100.Prepared grease
Stir 2 hours under mixed solution elder generation room temperature strongly, then ultrasound 2h at 40 DEG C, obtains water system oil hydrosol.Oil separates effect with water
Rate refers to content oily in the filtrate after separation compared to the mass percent that the content of oil before separation reduces.The separation effect of three kinds of oily phases
Rate is above 99.8%.And 5 DEG C, 25 DEG C, under 40 DEG C of solution and 3%, 10%NaCl solution, separative efficiency still above
99.8%, show wide actual application prospect.
Comparative example 1
The present embodiment, the difference lies in that in step 1, weighs 0.2 gram of PVDF-HFP in acetic anhydride with embodiment 1
In copper solution.The comparative example obtains being catenate nanofiber, and nanofiber film dynamic performance under this condition is poor.
Comparative example 2
The present embodiment, the difference lies in that in step 1, weighs 8 grams of PVDF-HFP in Salicylaldoxime with embodiment 1
In solution.Under the comparative example, concentration of dope is larger, and solution viscosity is larger, and spinning process is not smooth, obtain nanofiber compared with
It is difficult.
Embodiment 3
In step 4, the vial obturaged is moved into baking oven, temperature is 100 DEG C, time 5h.Under the comparative example,
Growth temperature is higher, and cupric oxide nano piece is quickly grown in film surface, and fiber film surface is easily caused to grow more copper oxide
Nanometer sheet, and can be relatively fewer inside film.It causes inside and outside film the growth of cupric oxide nano piece irregular, is unfavorable for filter process and filtering
Effect.
The present invention is exemplarily described in conjunction with attached drawing above.Obviously, present invention specific implementation is not by above-mentioned side
The limitation of formula.As long as using the improvement for the various unsubstantialities that the inventive concept and technical scheme of the present invention carry out；Or not
It is improved, above-mentioned conception and technical scheme of the invention are directly applied into other occasions, in protection scope of the present invention
Within.
Claims (8)
1. a kind of preparation method of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, which is characterized in that packet
Include following steps:
Salicylaldoxime is dissolved in binary organic solvent by step 1, and being added account for total solution mass fraction later is 10-20%'s
Kynoar-hexafluoropropene, it is agitated to obtain spinning solution, Salicylaldoxime and Kynoar-hexafluoropropene mass ratio
For 1:2-6；
The spinning solution is prepared organic/inorganic hybrid nano tunica fibrosa by method of electrostatic spinning by step 2；
The hybrid nano fibrous membrane is baked, cools down to obtain fiber surface and have copper oxide seed by step 3
Nano fibrous membrane；
The nano fibrous membrane that fiber surface has copper oxide seed is put into copper oxide growth-promoting media by step 4, sealed later,
50-60 DEG C reaction after, be cooled to room temperature to get；
The preparation method of the copper oxide growth-promoting media is that Salicylaldoxime is dissolved in water, and ammonium hydroxide is added dropwise later to precipitating all dissolutions
Up to transparent navy blue copper ammon solution.
2. super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film preparation method according to claim 1,
It is characterized in that, the Salicylaldoxime and Kynoar-hexafluoropropene mass ratio are 1:2-3.
3. super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film preparation method according to claim 1,
It is characterized in that, the device for spinning that the electrostatic spinning uses includes receiver board, solution tank, dials and for driving solution tank
Dials rotation driving motor, the technological parameter of electrostatic spinning include: apply voltage 20-30kV, receive distance be 15-
40cm, dials revolving speed 10-15r/min.
4. super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film preparation method according to claim 1,
It is characterized in that, the temperature baked in the step 3 is 100-120 DEG C, baking time 12-24h.
5. super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film preparation method according to claim 1,
It is characterized in that, the binary organic solvent is that n,N-Dimethylformamide and acetone form.
6. super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film preparation method according to claim 5,
It is characterized in that, the mass ratio of the n,N-Dimethylformamide and acetone is 1:1.
7. a kind of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, which is characterized in that use claim
Any one of 1-6 preparation method is made.
8. a kind of purposes of super hydrophilic nucleocapsid Kynoar hexafluoropropene/cupric oxide nano piece film, which is characterized in that for mentioning
High oil and water separation capability.
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