CN107158753A - It is firm, it is durable, can volume production the effective oil/water separation in the presence of a harsh environment of fluorine graft grapheme based super hydrophobic coating - Google Patents
It is firm, it is durable, can volume production the effective oil/water separation in the presence of a harsh environment of fluorine graft grapheme based super hydrophobic coating Download PDFInfo
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- CN107158753A CN107158753A CN201710427254.5A CN201710427254A CN107158753A CN 107158753 A CN107158753 A CN 107158753A CN 201710427254 A CN201710427254 A CN 201710427254A CN 107158753 A CN107158753 A CN 107158753A
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- 238000000576 coating method Methods 0.000 title claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000011248 coating agent Substances 0.000 title claims abstract description 77
- 238000000926 separation method Methods 0.000 title abstract description 40
- 230000003075 superhydrophobic effect Effects 0.000 title abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 8
- 239000011737 fluorine Substances 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000003618 dip coating Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000006260 foam Substances 0.000 claims abstract description 11
- 239000004743 Polypropylene Substances 0.000 claims description 66
- 229920000742 Cotton Polymers 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000004814 polyurethane Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 8
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- 239000011259 mixed solution Substances 0.000 claims description 2
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- 239000004575 stone Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 43
- 230000004907 flux Effects 0.000 abstract description 23
- 239000007762 w/o emulsion Substances 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000004094 surface-active agent Substances 0.000 abstract description 9
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- 235000019198 oils Nutrition 0.000 description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- 238000012360 testing method Methods 0.000 description 17
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- 239000000243 solution Substances 0.000 description 13
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
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- KWXGJTSJUKTDQU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-8-iodooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I KWXGJTSJUKTDQU-UHFFFAOYSA-N 0.000 description 3
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- 235000010777 Arachis hypogaea Nutrition 0.000 description 3
- 235000018262 Arachis monticola Nutrition 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- 230000006641 stabilisation Effects 0.000 description 3
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- 238000002411 thermogravimetry Methods 0.000 description 3
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical class NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 239000004332 silver Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229940073450 sudan red Drugs 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AAJQTWWVKREOQP-UHFFFAOYSA-N 4-oxo-4-pyren-1-ylbutanoic acid Chemical compound C1=C2C(C(=O)CCC(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 AAJQTWWVKREOQP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
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- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
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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
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention be it is firm, it is durable, can volume production the effective oil/water separation in the presence of a harsh environment of fluorine graft grapheme based super hydrophobic coating.Using simple, low cost, the material with special wetability efficiently is prepared with the method for being easily enlarged production, the effective oil/water separation used it under harsh conditions is still a huge challenge.The application is prepared for the graphene-based coating of fluorine grafting using simple dip-coating method.This coating can be resistant to the actual environment of harshness, such as boiling water, peracid, high-alkali and saturated salt solution.The foam of coating can absorb the oil in oil/water mixture, and with very high absorbability.Importantly, only under gravity, the film of coating can efficiently separate the stable water-in-oil emulsion of surfactant, with high cycle performance and great flux.The excellent performance (including durability, recuperability can production and adverse environment resistant etc.) of the coating has highlighted its practical application in terms of emulsion is separated and clears up oil spilling.
Description
Technical field
It is more particularly to firm the invention belongs to water-oil separating field, it is durable, can volume production fluorine graft grapheme based super hydrophobic
Coating effective oil/water separation in the presence of a harsh environment.
Background technology
Growing industry oil sewage and frequently oil spill accident are attributed to, water-oil separating has become a whole world
Sex chromosome mosaicism.Traditional oily water separation technique, for example, centrifuge, oil filter, flotation and coagulation etc., due to its low separative efficiency, the energy
Cost and complicated separate apparatus and be limited in actual applications.In addition, these technologies can not effectively carry out water-oil separating.If
It is a kind of effective ways for efficiently separating oil water mixture that meter, which prepares the material with special wetability,.In these materials, surpass
Hydrophobic super lipophilic material is proved to be good candidate.Based on this, people use different method (photoetching, electro-deposition, glue
Body is assembled, chemical vapor deposition and electrostatic spinning etc.) it is prepared for the artificial surfaces with splendid water resistance.For example, Lin etc. is reported
Road has double-deck super-amphiphobic/super-hydrophobic-oil loving nano fibrous membrane of unidirectional oily conveying capacity.Yu etc. has synthesized porous match somebody with somebody
Position polymer is as coating, to absorb oil from water.We organize the content by controlling random copolymer each component, are prepared for tool
There is the water-oil separating coating of pH responses；The selfreparing film for water-oil separating is prepared for also by the method for electrostatic spinning.
Although however, achieving many progress in terms of moistened surface behavior, these achievements are limited with some, such as complicated
With time-consuming preparation and reagent and the high cost of equipment, which has limited practical application.
In addition to above-mentioned limitation, because in machining, it is metallurgical, transport, emulsion is typically encountered in petroleum industry etc., so
It is also very heavy to design stable mechanical performance and there is the material of repellence to be used to separate oil emulsion/aqueous mixtures to complex environment
Want.Feng etc. is prepared for a kind of coated filter paper of hydrogel, can in highly acidic, alkalescence and salt environment in separate oil/
Aqueous emulsion.However, the major defect of the film is that its environmental suitability is weak, because after hydrogel water suction, being easily swelled and becoming
It is soft.The gel that Kanamori etc. has synthesized various cotton candy shapes is based on alkoxy silane, for inhaling at relatively high temperature
Receive organic solvent.But this gel is unable to oil-water separation emulsion.Although Jin etc., which is prepared for a kind of single-wall carbon nanotube membrane, to be used for
Water-in-oil emulsion is separated, flux is up to 100 000L m-2h-1bar-1And separative efficiency>99.95%.But single-walled carbon nanotube
High cost and this film of additional pressure limit be only applicable to laboratory separator.Therefore, by economical and effective and
The super hydrophobic surface that simple manufacturing process prepares new stable is still important demand, and it is expected not only in severe reality
Under the conditions of be stable, but also to be kept completely separate oil/water mixture, oil/water breast particularly stable for surfactant
Liquid.
The content of the invention
In order to overcome above-mentioned deficiency, the present invention provides a kind of perfluoroalkyl grafting that can separate oil/water in the presence of a harsh environment
Graphene composite coating.Producible dip-coating method is soaked by low cost and solution, by fluorine graft grapheme (f-rGO) and oxygen
The coating that change 1- pyrenes butyric acid (OPBA) is constituted as molecular glue can densely stick to commercial materials such as polypropylene (PP) film, cotton
Cloth and polyurethane (PU) foam (Fig. 1).Compared with the super wet material reported in the past, our super-hydrophobic coat has more extensive
Advantage, be included in bonding strength extremely strong on base material and overbased acidic, the great repellency of alkalescence and saturated salt solution and
Economic and convenient preparation method.Importantly, coat film shows only have extremely strong surfactant under gravity
The high separating efficiency of stable water-in-oil emulsion and greatly separate flux.
To achieve these goals, the present invention is adopted the following technical scheme that：
Separate and applied in oil/water in the presence of a harsh environment the invention provides perfluoroalkyl graft grapheme coating (f-rGO).
Present invention also offers a kind of compound painting of perfluoroalkyl graft grapheme that can separate oil/water in the presence of a harsh environment
Layer, including：
Substrate；
Aoxidize 1- pyrenes butyric acid (OPBA) tack coat；
Perfluoroalkyl graft grapheme coating f-rGO.
It is preferred that, the substrate is polypropylene (PP) film, cotton or polyurethane (PU) foam.
It is preferred that, described f-rGO, OPBA mass ratio are 1:0.35~0.5, most preferably, described f-rGO, OPBA's
Mass ratio is 1：0.5.
It is preferred that, the quality of the substrate is the 90%~95% of composite coating gross mass, and research is found：When the weight of coating
When amount reaches more than the 5% of gross weight, expected water-oil separating performance can be obtained.
The perfluoroalkyl graft grapheme composite coating of oil/water can be separated in the presence of a harsh environment present invention also offers a kind of
Preparation method, including：
Perfluoroalkyl graft grapheme f-rGO dispersion liquids are well mixed with oxidation 1- pyrenes butyric acid (OPBA) dispersion liquid, obtained
Mixed liquor；
Base material is immersed into above-mentioned mixed liquor dip-coating uniformly, dries, produces.
It is preferred that, in the mixed solution, f-rGO mass concentration is 0.06~0.066mg/ml, the matter of the OPBA
Amount concentration is 0.03~0.033mg/ml.
It is preferred that, the solute of the mixed liquor is ethanol.
It is preferred that, the base material is polypropylene (PP) film, cotton or polyurethane (PU) foam.
Present invention also offers the perfluoroalkyl that can separate oil/water in the presence of a harsh environment grafting prepared by any above method
Graphene composite coating.As shown in Figure 1.In the process, OPBA is used as the molecule glue of connection f-rGO and different substrates.Apply
Layer is easily enlarged preparation, and can tolerate severe actual environment.
Beneficial effects of the present invention
(1) present invention is sticked the graphene that fluorine is grafted using OPBA as molecule adhesive water by simple dip-coating method
It is attached to including business PP films, multi-functional super-hydrophobic super-oleophylic material is prepared on cotton and PU foams.And these materials can be with
It is resistant to harsh physical condition, such as boiling water, strong acid, highly basic and saturated salt solution.Importantly, only under gravity, the PP of coating
Film can efficiently separate the stable water-in-oil emulsion of surfactant, and have high separation flux.In addition, coating
PU foams also have high oil absorption and recyclability energy.The present invention can be effective by such a method prepares coating method
Ground separates the oil spilling produced in a series of stable emulsion of surfactants and cleaning industry and daily life.
(2) preparation method of the present invention is simple, separative efficiency is high, practical, it is easy to promote.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not constitute the improper restriction to the application.
Fig. 1 is preparation process schematic diagram of the f-rGO/OPBA coatings on different substrate materials.
Fig. 2 is different coating state diagram, wherein, (a) be different quality than f-rGO/OPBA coatings water contact angle
(CA) change；(b), (c) is the SEM image of uncoated PP films and the PP films of f-rGO/OPBA dip-coatings；(d) it is to drop in water droplet
Dynamic contact angular measurement figure on uncoated PP films：(f) it is the dynamic contact angle that drops in hexane drop on the PP films of coating
Measurement figure；(e), (g) is to be connect in air (e) with the dynamic on the PP films that water droplet is dropped in coating respectively in n-hexane (g) respectively
Feeler measurement figure.
Fig. 3 is the phenogram that f-rGO is successfully synthesized.Wherein (a) is XRD；(b) it is the infrared figure of Fourier；(c) it is EDS
Figure.
Fig. 4 is the TGA test charts that PP films and f-rGO/OPBA coat PP films.
Fig. 5 is the performance test figure of different films, wherein, (a) is that f-rGO/OPBA coating PP films soak under fast stirring
Enter the stability diagram in 100 DEG C of hot water；(b) it is to be soaked when in aggressive solvent such as 6M HCl, 6M NaOH and saturation NaCl solution
When steeping 24 hours, the water CA measured values of the PP films of coating；Its illustration is 6M HCl, the 6M NaOH on the PP films of coating and satisfied
With the photo of NaCl drops；(c) be with hand rub 1000 times coating PP films mechanical endurance；Its illustration is mechanical friction
Photo after 1000 times；(d) be the PP films coated under oily (such as n-hexane and dichloromethane) stability diagram；Its illustration is
The photo of the water droplet on PP films coated under oil.
Fig. 6 is f-rGO/OPBA coating PP films water-in-oil emulsion separation test chart.Wherein, (a) is dichloromethane bag water and milk
Liquid separation process；(b), (c), (d) is dichloromethane Bao Shui respectively, and toluene bag water and peanut water-in-oil emulsion separate front and rear
DLS test charts.
Fig. 7 is bag aqueous emulsion experimental analysis figure；Wherein, (a) is the peanut water in oil emulsion of the span80 stabilizations before and after filtering
The optical microscope image of liquid；(b), (c) is to chloroform bag aqueous emulsion (b) and span80 stabilization stable span80 respectively
Vapour water-in-oil emulsion (c) filtered before and after (illustration) drop size DLS test charts；(d) be by using
Dichloromethane bag aqueous emulsion stable span80 as example the view for expanding separation.
Fig. 8 is water-in-oil emulsion separating experiment figure, wherein, (a) is that the stable water-in-oil emulsions of various span80 are separated
Flux and content of residual water figure；(b) it is the W/Di emulsion stable by separating span80, is coated after washing 20 circulations with ethanol
PP films cycle performance test result figure；(c), (d) is that machinery rubs after 1000 times (c) and is dipped into 6M HCl respectively respectively
The mechanically and chemically endurance measurement figure for the PP films that 24 hours (d) is coated afterwards.(e), (f) is separation oil bag 6M respectively
Flux (e) and residual moisture content (f) figure after HClaq emulsions, 6M NaOHaq emulsions and saturation NaClaq emulsions.
Fig. 9 is the super-hydrophobic super-oleophylic figure of f-rGO/OPBA coated cotton fabrics.Wherein (a), (b) be respectively original cotton and
The SEM phenograms of coated cotton fabric；(c) be coated cotton fabric super-hydrophobic static contact angle figure；(d), (e) be respectively original cotton and
The wetability photo directly perceived of coated cotton fabric；(f) be coated cotton fabric lipophile static contact angle figure.
Figure 10 is the chemical stability and mechanical stability test chart of coated cotton fabric.Wherein, (a) is that different pH are water-soluble
The static contact angle test chart of liquid；(b) be in the different pH aqueous solution soak different time water contact angle test chart；(c) it is
The contact angle test chart of different time is boiled in boiling water；(d) it is the contact angle test chart of rubbing different number of times.
Figure 11 is the super-hydrophobic super-oleophylic figure of f-rGO/OPBA coating PU sponges.Wherein, (a), (b) is original sea respectively
The SEM phenograms of tender coating sponge；(c) be coating sponge silver mirror phenomenon, it was demonstrated that its super-hydrophobicity；(d) it is coating sponge
Lipophile static contact angle figure；(e) be coating sponge roll angle test chart.
Figure 12 is coating absorbability test chart, wherein, (a), (b) they are the PU foams of f-rGO/OPBA coatings respectively in water
Upper (a) absorbs n-hexane and (b) absorbs the photo of dichloromethane under water；(c) be coating PU sponges to different organic solvents and
The absorbability figure of oil；(d) it is that the PU foams of coating are circulated to the absorbability of chloroform schemes by extruding after 100 circulations.
Embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
Embodiment 1
1. experimental section
1.1 material
Natural graphite flakes (8000 mesh, purity 99.95%), perfluoro octyl iodide and 4- Iodoanilines are provided by Aladdin；Dense sulphur
Sour (mass fraction 95-98%), concentrated hydrochloric acid (mass fraction 36-38%), potassium permanganate and copper analysis are pure, purchased from Beijing Chemical Plant
(China).Hydrogen peroxide (H2O2) and sodium nitrate by Laiyang Shi Kang chemical companies provide.OPBA(4-Oxo-4-Pyren-1-yl-
Butyric Acid) it is purchased from Mayan century.Polypropylene (PP) film, cotton and polyurethane (PU) foam are bought from local shop.
The preparation (Rf-NH2) of 1.2 pairs of perfluoro capryl aniline
By perfluoro octyl iodide (5.46g, 0.01mol), 4- Iodoanilines (1.46g, 0.0067mol) and copper (1.28g,
0.02mol) agitating and heating 12 hours at 120 DEG C of the dispersion in 25ml DMSO, are connected to the 100ml of reflux condenser
In flask.The cupric iodide and excessive copper of generation is removed by filtration.10ml water and 10ml ether are added into filtrate.By ether layer
It is washed with water for several times to remove DMSO and perfluoro octyl iodide, then using petroleum ether and ethyl acetate (volume ratio 15:1) it is used as and washes
De- liquid (1.2g, yield：35.3%) column chromatography eluting product is passed through.1H-NMR (chloroform-d)：4.23 (br s, 2H), 7.54
(d, J=8.8Hz, 2H), 7.72 (d, J=8.8Hz, 2H).
The preparation of 1.3 perfluoroalkyl graft graphemes (f-rGO)
Using Hummers methods graphene oxide (GO) is prepared from native graphite.By GO (0.6g) and 4- (perfluoro capryl)
Aniline (0.9g) is added to the three-necked flask of 90ml ethanol.Mixture is stirred at reflux 24 hours at 100 DEG C.Then by gained
Solution is 0.22 μm of PP membrane filtrations by average pore size.The powder of filtering is cleaned 5 minutes with ultrasonic wave in 100ml ethanol
Rinsing, is then filtered.Rinsing filtering is repeated 4 times to remove 4- (perfluoro capryl) aniline of Physical Absorption.Finally, it is configured to one
Determine the f-rGO alcohol dispersion liquids of concentration.
The manufacture of 1.4f-rGO/OPBA coating materials
The f-rGO/OPBA coating materials of super-hydrophobic super-oleophylic are prepared using dip coating.By 4ml f-rGO ethanol solutions
(1mg/ml) and 2ml OPBA ethanol solutions (1mg/ml) are added in 60ml ethanol, stir about 20 minutes, are formed dispersed
Solution.PP films or cotton or PU foams are put into above-mentioned solution about 1 hour under agitation, and done in 100 DEG C of baking oven
Dry 1 hour.
The preparation of the stable water-in-oil emulsion of 1.5 surfactants
For the water-in-oil emulsion that all span80 are stable, 0.35g span80 are added separately to 57mL chloroforms,
In gasoline, dichloromethane, n-hexane, toluene and peanut oil, 1mL water is then added.Stir the mixture for 3 hours.All emulsions
Stablize at ambient conditions more than 1 week.
2. emulsion separating experiment
Oil/water emulsion separating experiment is carried out by separator.Whole separation process is only by weight-driven.It is logical in order to measure
Amount, the various emulsions of 30mL are poured into separator.The time of 10mL liquid in the middle of after record separation, and painting is calculated according to the following formula
The separation flux of film：
Flux=V/St
Wherein, V (L) is the volume after separation, S (m2) be film effective area, t (h) is the testing time.Use Karl
Water content after the separation of Fischer moisture titration measuring.
3. instrument and sign
FTIR spectrograms are obtained on FTIR spectrum instrument IR Prestige-21 (Shimadzu, Japan).In D-
The test of X-ray diffraction (XRD) is carried out on 8ADVANCE X-ray diffractometers (Bruker AXS, Germany).In SDT Q600
Thermogravimetric analysis (TGA) is carried out on (TA, USA).(EDX) spectrum test is carried out by SEM (SEM, S-4700).
The pattern of coating material is worked sign by SEM (S-4700) under 20kV.Pass through light microscope (BM2000) and dynamic optical
Scatter the diameter distribution of (DLS) measurement (ZEN3690, Germany) observation emulsion droplet.Use contact angle meter (DSA30, USA)
Measurement surface contact angle.For contact angle test, volume is dropped on the surface of coating material for 3.0 μ L drop, and is checked
At least three different sample areas are to obtain mean exposure angle value.Using Karl Fischer moisture titrations (WS-3000,
Micro-water analyzer, Zibo, China) determine the water content after separation.
4. result is with discussing
The present invention is prepared for f-rGO by the reaction of 4- (perfluoro capryl) aniline and graphene oxide.In dip coating process,
OPBA connects f-rGO and substrate as molecule glue.In order to prove OPBA key effect, by different quality than f-rGO
It is dispersed in OPBA in ethanol solution.Business type PP films are used as verifying first the substrate of conceptual approach.As shown in Figure 2 a, in PP
On film dip-coating different quality than f-rGO/OPBA after water contact angle (CA) change.When f-rGO/OPBA mass ratio is 1:
0.5, obtain the PP films that water CA is 163.7 °.Due to OPBA water-wet behavior, the further increase of OPBA contents causes water CA to drop
Low (Fig. 2 a).Therefore, we select f-rGO/OPBA mass ratio to be 1：0.5 coating is used for subsequent experimental.
Typical SEM (SEM) image shows the smooth surface (Fig. 2 b) of uncoated PP films.Dip-coating f-
After rGO/OPBA, corrugated f-rGO sheet materials are firmly sticked on the surface of PP films (Fig. 2 c).Ring is swept electro microscope energy spectrum instrument (EDX) and shown
Show the element F (Fig. 3 c) of the f-rGO on fiber surface, show that f-rGO/OPBA is successfully coated on PP films.Pass through thermogravimetric point
The amount of analysis estimation f-rGO/OPBA coatings is about 5wt% (Fig. 4).According to the Cassie models drawn from Young's equation, we recognize
For special wetability is attributed to classification micro-and nano-structural surface and f-rGO/OPBA coatings.
In order to check the dynamic moisture behavior of water and oil on film, sprawling for drop is recorded using high speed camera system
Journey.When water droplet (3uL) is contacted with uncoated PP films, it spreads rapidly and penetrated into one second in film, and water CA is about
For 0 ° (Fig. 2 d).On the contrary, when water droplet is forced fully to contact and then lift with the surface of coating, water droplet is several when leaving film surface
Do not deform, showing the PP films of coating has super-hydrophobicity, with ultralow adhesiveness (Fig. 2 e).When 3uL oil droplets, (n-hexane is made
For example) with f-rGO/OPBA coat PP films contact when, it is penetrated into film immediately, show film super oil-wet behavior (figure
2f).It is furthermore interesting that, when water droplet is contacted under n-hexane with the PP films of coating, drop does not still become when leaving surface
Shape (Fig. 2 g), different from the superoleophobic property of fluorinated surface, its superoleophobic property is deprived of when contacted, causes oil repellent to reduce.
Super-hydrophobicity potentially contributes to the high flux of water-in-oil emulsion separation in oil.
It is metallurgical in view of waste water generally in machinery, transport, produced in the complex environment such as petroleum industry, unique coating should
This bears severe condition, without losing super-hydrophobicity.Therefore, f-rGO/OPBA coatings are detected under various harsh conditions
Stability.Fig. 5 a show water CA change of the PP films of f-rGO/OPBA coatings with vigorous stirring in boiling water (100 DEG C).Leaching
Enter in boiling water after 24 hours, water CA remains above 150 °, showing the PP films of coating has high-temperature stability (Fig. 5 a).Except hot water resistance
Outside, the PP films of f-rGO/OPBA coatings are in strong acid, and highly basic and saturated salt solution are highly stable.In 6M HCl, 6M NaOH and saturation
After immersion is up to 24 hours in NaCl solution, almost unchanged (the water CA of static contact angle>148 °), show the PP films of coating in corrosion
Property solution in have good stability (Fig. 5 b).
In order to test the bonding strength between f-rGO/OPBA coatings and substrate, we have rubbed the PP films of coating with hand,
And it was defined as fatigue and cyclic (Fig. 5 c by 15 seconds.By 1000 rub cycles, the surface texture of the PP films of coating is shown
Slight change, and PP films remain in that hydrophobicity, and water CA is 143 °, shows the perfect mechanical stability of film.Oil is lower super
The stability of hydrophobic property is also by the PP films of coating are immersed in different organic solvents, in the contact angle of different time sections
Change to measure.N-hexane and dichloromethane are immersed in after 3 days, water CA is kept approximately constant (Fig. 5 d).It is super-hydrophobic under the oil of film
Property superstability and report surface hydrophobic in atmosphere it is entirely different because these hydrophobic surfaces lose it under oil
Hydrophobic performance.
Next, separating oil/water emulsion using the PP films of tough and tensile corrosion resistant f-rGO/OPBA coatings.Prepare with micro-
Rice and the stable emulsion of the surfactant of nano level emulsion droplet size.Emulsion is placed in room temperature environment not to be observed more than 1 week
To demulsification or precipitation, show that emulsion has good stability.The f-rGO/OPBA PP films coated are fixed on two vertical glass
Between glass pipe (Fig. 6 a).The size of all emulsions is in the range of hundreds of nanometers to several microns.Correspondingly, in the filtrate of collection
In, the presence (Fig. 7 a) by observation by light microscope less than emulsion droplet.In addition, DLS tests show the drop chi before and after separation
It is very little to obtain difference.Emulsion particle diameter before separation changes between 100nm to 2 μm, and the particle diameter after separating is in 4-8,3-6,5-9,3-
Chloroform Bao Shui (span80-W/Tr) stable span80 in the range of 10,10-13 and 5-10nm, vapour stable span80
Water-In-Oil (span80-W/G), dichloromethane Bao Shui (span80-W/Di) stable span80, toluene Bao Shui stable span80
(span80-W/T) n-hexane Bao Shui (span80-W/H) stable span80, peanut Water-In-Oil (span80- stable span80
W/P) (Fig. 7 b, c, Fig. 6 b-d, table 1), shows that the PP films of coating can be with high-quality separation emulsion.
The separating resulting of the different emulsions of table 1.
Prepared in view of the surface of f-rGO/OPBA coatings, measure the separation of 1L emulsions.As shown in figure 7d, by f-rGO/
A diameter of 4cm film is fixed between two vertical glass tubes by the dip-coating of OPBA dispersions on PP films.Emulsion is poured on film
After upper, it was observed that transparent filtered solution, and the separation of the W/Di emulsions of 1Lspan80 stably was completed using about 33 minutes.
Even if it is worth noting that, the size that the PP films of coating can separate all emulsion emulsion droplets is less than coating
The aperture of PP films.This is the size based on coarse separation rather than screening filtering mainly due to separation, and it passes through the painting with film
The coalescence of the drop of layer contact intercepts emulsion droplet.
Economically set out, separation flux is separation emulsion very important parameter.It is nearly completely separated by measurement
The time of the emulsion of certain volume determines the flux of the various emulsions for the PP films for penetrating through coating.As shown in Figure 8 a, for
Span80-W/Di, span80-W/G, span80-W/Tr, span80-W/T, span80-W/H obtain 1395,885,1332,
1011,1026Lm-2h-1Separation flux (table 1).It should be noted that whole separation process only by weight-driven without appointing
What external force.The flux obtained is highest value (table 1) compared with reporting result, and is the tradition with similar permeance property
Several times of filter membrane.
It is this in terms of energy-conservation compared with traditional filter membrane in view of only by separating emulsion under weight-driven
Separating property is very attractive, because traditional filter membrane such as milipore filter usually requires one to several bar transmembrane pressure
Power separates come the emulsion realized.Oily purity after first separation in filtrate is also detected with Karl Fischer analyzers.As schemed
Shown in 8a, the content of residual water in filtrate is between 17-22ppm, it is shown that the high score of the PP films of f-rGO/OPBA coatings is from effect
Rate.The penetration by water pressure for showing the maximum height for the liquid that film can be supported is one of important parameter of practical application.By making
The breakthrough pressure that the PP films of coating are measured with vavuum pump is about 0.2bar.Water-column of this pressure equivalent to 2.0 meters.
Conventional super-hydrophobic/super-oleophilic water-oil separationg film not only has the mechanical stability of difference, but also there is surface
The shortcoming of pollution.In order to measure the cycle performance energy of film, the separation flux of the PP films of coating is measured.As shown in Figure 8 b, every
After secondary separation emulsion, film is simply washed with ethanol and separates flux to recover it.As can be seen that flux is completely extensive after cleaning
Multiple arrive starts flux, is also had almost no change with the increase of period.After 20 circulations, flux still keeps 1310L m-2h-1
Relative high levels, residual moisture content is maintained at 16ppm.This shows the excellent recyclable property of film, and this is for practical application
It is very important.
Coat the test of the mechanical performance and chemical stability of PP films.We rub the PP film machineries of f-rGO/OPBA dip-coatings
After rubbing with the hands 1000 times, oil hydrosol separation is carried out.The mechanical performance of film is determined by measuring the water content of separation flux and filtrate
With chemical stability (such as Fig. 8 c, d).Flux after water-in-oil emulsion separation stable all span80 does not find obvious drop
It is low, and filtrate water content also without obvious rise, this shows that coat film has very high mechanical stabilizability.Will in addition, working as
The water content carried out again after 24 hours in oil hydrosol separation, separation flux and filtrate in the film immersion 6M HCl of coating does not have yet
Change, shows that coating PP films still have very high separative efficiency in the presence of a harsh environment.Importantly, we are not also by using
Emulsion is prepared with oil and 6M HCl, 6M NaOH and the saturation NaCl aqueous solution.As shown in Fig. 8 e and Fig. 8 f, for different oil
Wrap for 6M HClaq, 6M NaOHaq and saturation NaClaq, separation flux stills remain in 800-1500L m-2h-1, in filtrate
Content of residual water all in the range of 18-32ppm, show that coating PP films have very high separative efficiency.
Next, we using business cotton as substrate further to confirm the superiority of f-rGO/OPBA coatings.Such as
Shown in Fig. 9, f-rGO/OPBA successfully dip-coating on the surface of cotton.Contact-angle measurement shows the super-hydrophobic/super of coated cotton fabric
Oleophilic properties.When the cotton for being coated with f-rGO/OPBA is immersed in corrosive solution (such as pH=1 and 13 aqueous solution) 1 hour
When, water contact angle has almost no change (Figure 10 a, 10b).In addition, by being placed in boiling water and carrying out machinery by the cotton of coating
Experiment is rubbed, to prove the stability of coated cotton fabric.The stability of water CA measurements shows between f-rGO/OPBA and cotton surface
It there is very strong bonding force (Figure 10 c, 10d).
In order to further prove the multifunctional application of f-rGO/OPBA coatings, f-rGO/OPBA, which is also immersed, is coated in business PU bubbles
Oil/water separation is carried out on foam.After being immersed in f-rGO/OPBA alcoholic dispersions, whole PU is full of solution.In SEM image
In, it can clearly be seen that after dip-coating, the surface of PU foams is changed into having submicron-scale from smooth surface (Figure 11 a)
Random rough surfaces (Figure 11 b).The sponge of the PU sponges of non-dip-coating and coating is placed in water, coating PU foams can be observed
The phenomenon of similar silver mirror, this is due to coat to form interface between PU sponges cladding air and the water of surrounding and produce mirror-reflection
(Figure 11 c).The PU of f-rGO/OPBA coatings has been further demonstrated that by the oily CA and water droplet that test n-hexane small slip angle
The super-hydrophobic super-oleophylic (Figure 11 d, e) of foam, this becomes the ideal material of the greasy dirt and organic solvent that remove in waste water.
When the PU foams of f-rGO/OPBA coatings are contacted with hexane layer (with the Sudan's red colouring) waterborne, it can be complete
Rapidly absorb hexane (Figure 12 a).In addition, the PU foams of coating can also absorb dichloromethane (using the Sudan's red colouring) under water
(Figure 12 b).Absorbability quantitative scoring is at last by absorbing the PU sponges weight of liquid with the ratio of dried PU foams come really
Fixed.We have studied coating PU sponges to various organic liquids and oils (including diesel oil, gasoline, ethyl acetate, dichloromethane
Alkane, chloroform, toluene, peanut oil and n-hexane) absorption.These materials be in our daily lifes and industry in common dirt
Contaminate thing.The PU foams of f-rGO/OPBA coatings all show very high absorbability to all above-mentioned organic liquids and oil.Apply
The PU foams covered can absorb 30 to 82 times of its own weight of oil and organic solvent (Figure 12 c).These values are far above previous
The absorbability of the adsorbent of report, such as wool non-woven fabrics (9-15 times), polymer (5-25 times), nano wire film (4-20 times),
The CNT sponges (25-125 times) of spongy graphene (20-86 times) and the boron that adulterates.In addition, the PU foams of coating is good
Cycle performance.As shown in Figure 12 d, after 100 absorption-extrusion cycles, the significant change of absorbability, table is not observed
The PU foams of bright f-rGO/OPBA coatings have absorption and the recycling performance of stabilization.Therefore, f-rGO/OPBA coatings PU steeps
Foam be it is a kind of promise to be a kind of adsorbent to one's profit, for removing pollutant.
5. conclusion
In a word, by simple dip-coating method, the graphene that fluorine is grafted is attached to using OPBA as molecule adhesive water
Including business PP films, multi-functional super-hydrophobic super-oleophylic material is prepared on cotton and PU foams.And these materials can be resistant to
Harsh physical condition, such as boiling water, strong acid, highly basic and saturated salt solution.Importantly, only under gravity, the PP films of coating can
Efficiently to separate the water-in-oil emulsion that surfactant is stable, and there is high separation flux.In addition, the PU bubbles of coating
Foam body also has high oil absorption and recyclability energy.It is contemplated that, we can be with by such a method prepares coating method
Efficiently separate the oil spilling produced in a series of stable emulsion of surfactants and cleaning industry and daily life.
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. perfluoroalkyl graft grapheme coating (f-rGO) separates applied in oil/water in the presence of a harsh environment.
2. a kind of can separate the perfluoroalkyl graft grapheme composite coating of oil/water in the presence of a harsh environment, it is characterised in that bag
Include：
Substrate；
Aoxidize 1- pyrenes butyric acid (OPBA) tack coat；
Perfluoroalkyl graft grapheme coating f-rGO.
3. coating as claimed in claim 2, it is characterised in that the substrate is polypropylene (PP) film, cotton or polyurethane
(PU) foam.
4. coating as claimed in claim 2, it is characterised in that described f-rGO, OPBA mass ratio are 1:0.35~0.5.
5. coating as claimed in claim 2, it is characterised in that the quality of the substrate for composite coating gross mass 90%~
95%.
6. a kind of preparation method for the perfluoroalkyl graft grapheme composite coating that can separate oil/water in the presence of a harsh environment, it is special
Levy and be, including：
Perfluoroalkyl graft grapheme f-rGO dispersion liquids are well mixed with oxidation 1- pyrenes butyric acid (OPBA) dispersion liquid, must be mixed
Liquid；
Base material is immersed into above-mentioned mixed liquor dip-coating uniformly, dries, produces.
7. method as claimed in claim 6, it is characterised in that in the mixed solution, f-rGO mass concentration for 0.06~
0.066mg/ml, the OPBA mass concentration are 0.03~0.033mg/ml.
8. method as claimed in claim 6, it is characterised in that the solute of the mixed liquor is ethanol.
9. method as claimed in claim 6, it is characterised in that the base material is polypropylene (PP) film, cotton or poly- ammonia
Ester (PU) foam.
10. prepared by any one of claim 6-9 methods described can separate the perfluoroalkyl grafting stone of oil/water in the presence of a harsh environment
Black alkene composite coating.
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