CN103357276A - UV cured super-hydrophilic and underwater super-oleophobic oil-water separation membrane, its preparation method and application thereof - Google Patents
UV cured super-hydrophilic and underwater super-oleophobic oil-water separation membrane, its preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a UV cured super-hydrophilic and underwater super-oleophobic oil-water separation membrane, its preparation method and an application thereof. The preparation method comprises the following steps: carrying out ultrasonic cleaning on a fabric silk screen; preparing nano sol by a sol-gel method, mixing 10-50 parts of a single-function UV cured oligomer, 60-80 parts of a bi-functional UV cured oligomer, 10-20 parts of multifunctional UV cured oligomer, 200-500 parts of silica sol, 1-5 parts of a waterborne photoinitiator and 1-5 parts of an emulsifier, and uniformly dispersing; coating a mixed liquor on the surface of a membrane by a dip-coating or spray process, drying, and carrying out UV curing to obtain a product. The surface of the oil-water separation membrane has a hydrophilic polymer molecular brush structure based on the micro-nano dual structure. The contact angle of the membrane to water and oil is 0 degree in the air, and the membrane has super-hydrophilicity. The contact angle of the membrane to oil drops is greater than 150 degrees underwater, and the membrane has low adherence to oil drops. The membrane provided by the invention can be used in separation of an oil-water mixture and treatment of oily sewage.
Description
Technical field
The present invention relates to a kind of UV-curable waterborne coatings, particularly relate to a kind of have in the air super parents and the water-oil separating nethike embrane and its preparation method and application of super oleophobic properties under water, belong to photo-curing material and organic-inorganic hybrid nanometer technical field of function materials.
Background technology
Since Gulf of Mexico oil accident in 2010, started the upsurge of this global problem of oily waste water treatment.The oil-polluted water wide material sources, in industries such as oil, chemical industry, iron and steel, coking, gas generating station, machine-building and food processings, every water that directly contacts with oils all contains oil.Oil has the difference of polar oil and non-polar oil, and polar oil derives from animal, and is biodegradable; Non-polar oil derives from oil and other mineral resources, then difficult for biological degradation.Oil is across the sea floating, diffuses to form rapidly the reoxygenation effect that the air-locked oil film of one deck hinders water body, affects the halomereid growth, destroys the marine ecology balance.Super hydrophilic super oleophobic film have in the air super hydrophilic, super hydrophilic super oleophobic properties in the water, when oily waste water contact membranes surface, under the stimulation of water film surface occur re-assemble by super-hydrophobic become super hydrophilic, thereby water can only down permeate under gravity and capillary force effect endlessly, and the surface remains super oleophobic property, thereby oil is stayed the effect that the surface reaches water-oil separating always, and because the potential oil repellency of film, oil all the time can't polluted membrane the surface, be a kind of real antipollution, Non-energy-consumption, long-life, high efficiency diffusion barrier.And when the surface of film has the hydrophilic polymer molecule brush, the surface hydrophilicity of film can be better, simultaneously, because the hydrophilic polymer molecule brush is in the structure of full extension in water, thereby make the surface of film on the basis with micro-nano binary coarse structure, have again nano level fluff structures, thereby the automatically cleaning effect with similar lotus leaf surface has " upspringing " effect to greasy dirt.
Publication number is that the Chinese invention patent application of CN102029079A discloses and has the oil-water separating net of super oleophobic properties under water, although this netting gear has oil-water separation, but the preparation of this film needs light initiation polymerization, different from the UV curing technology, the reaction time of this patent report is 60～100min, and the preparation method is simple not, and contains acrylic compounds volatile reactive diluent, skin, mucous membrane and eyes there are excitant, and cause larger VOC.Publication number is that the Chinese patent application of CN102716676A discloses with shitosan preparation and has the method for the oil-water separating net of super oleophobic properties under water, does not still relate to organic inorganic hybridization.And these two used film forming matters of patent all are complete water-soluble polymer, cause the resistance to water of nethike embrane relatively poor.
Summary of the invention
The object of the invention is to prepare a kind of have in air and under water the super hydrophilic while under water the profit UV of super oleophobic properties solidify super hydrophilic super oleophobic water-oil separating film and preparation method thereof under water that reaches.
Another purpose of the present invention provides UV and solidifies the super hydrophilic and application of super oleophobic water-oil separating film in the water-oil separating of separating oil aqueous mixtures and processing oil-polluted water under water.
Of the present invention have super hydrophilic and under water the water-oil separating nethike embrane of super oleophobic properties be as base material with 100～300 purpose screen of fabric, adopt the method for dip-coating or spraying to adsorb one deck water-based UV curing hybridization coating in the above, then with ultraviolet light polymerization, make it be coated with the hydrophilic polymer clad that is doped with inorganic nano-particle of micron thickness, simultaneously have the projection of nanoscale at clad, thereby obtain a kind of super hydrophilic water-oil separating nethike embrane of super oleophobic under water that reaches.
Water-oil separating nethike embrane of the present invention has the composite construction of special nanometer and micron, the mesh of micro-meter scale, the You Ji of micron thickness ?the raised structures of nano-scale on inorganic doping clad and the clad, water-oil separating nethike embrane of the present invention is 0 ° at air to water and oily contact angle, but has under water super oleophobic properties.
The object of the invention is achieved through the following technical solutions:
UV solidifies the super hydrophilic preparation method of super oleophobic water-oil separating film under water that reaches, and comprises the steps:
(1) with 100～300 purpose screen of fabric ultrasonic cleaning, normal temperature dries;
(2) Cai with Rong Jiao ?gel method, take tetraethoxysilane, tetramethoxy-silicane or purity titanium tetraethoxide as raw material, with alcohols and water in mass ratio 1:5～5:1 be mixed with cosolvent, with raw material and cosolvent in mass ratio 1:1～1:5 be mixed in 20～80 ℃ of waters bath with thermostatic control, stirring, behind 5～10min, drip catalyst, insulation 4～5h namely obtains Nano sol; Described alcohols is one or more in ethanol, propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol and the isobutanol; Described catalyst is hydrochloric acid, nitric acid, boric acid, sulfuric acid, ammoniacal liquor, sodium acid carbonate or NaOH;
(3) 10～50 parts of simple function UV are solidified oligomer, 60～80 parts of difunctionality UV curing oligomer; 10～20 parts of multifunctional UV solidify oligomer, the Nano sol of 200～500 parts of steps (2) gained, 1～5 part of light trigger and 1～5 part of emulsifying agent and mix, and disperse 10～20min with ultrasonic dispersion or disk dispersion machine under 1000～2000r/min; Get the UV solidified aqueous coating; It is methoxy polyethylene glycol acrylate or methoxy polyethylene glycol methacrylate-styrene polymer that described simple function UV solidifies oligomer; It is polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, water soluble acrylic acid ester oligomer, aqueous polyurethane acrylate oligomer, waterborne polyester acrylate oligomer or waterborne epoxy acrylate oligomer that described difunctionality UV solidifies oligomer; It is ethoxyquin trimethylolpropane triacrylate, water soluble acrylic acid ester oligomer, aqueous polyurethane acrylate oligomer, waterborne polyester acrylate oligomer or waterborne epoxy acrylate oligomer that described multifunctional UV solidifies oligomer; Described light trigger be water-soluble photoinitiator Darocur2959, Esacure KIP150, Irgacure891DW, QTX, BTC, BPQ, WB ?4784, WB ?4785, WB ?4789 or WB ?4792; Described emulsifying agent is neopelex;
(4) with in the UV solidified aqueous coating in the silk screen immersion step (3) that obtains in the step (1), behind immersion 5～20min it has vertically been lifted, perhaps adopted high-pressure spray gun directly the UV solidified aqueous coating to be sprayed on the silk screen; With soak or spraying after silk screen hang over and maintain the temperature at 80～120 ℃ of oven dry in the constant-temperature vacuum baking oven, then under uv cure machine, solidify 3～5min, get the super hydrophilic and water-oil separating nethike embrane of super oleophobic under water.
Preferably, described screen of fabric is stainless steel cloth, copper mesh, aluminium wire netting, nylon mesh, polyvinyl silk screen, aramid fiber silk screen, terylene silk net or acrylic fibre fabric web.The supersonic frequency of described ultrasonic cleaning is 20～40KHz, and power bracket is 100～150W.The supersonic frequency of described ultrasonic dispersion is 20～40KHz, and power bracket is 300～500W.Then described ultrasonic cleaning with absolute ethyl alcohol or acetone ultrasonic cleaning, uses the distilled water ultrasonic cleaning clean for clean with ultrasonic washing with clean water first again.The speed of described dropping catalysis is 1～10ml/min; The ultraviolet wavelength of described uv cure machine is 245～405nm.Nano particle diameter in the described Nano sol is controlled at 10～500nm, and the nano particle mass content is 20～35%.
The super hydrophilic water-oil separating nethike embrane of super oleophobic under water that reaches, it is made by above-mentioned each described preparation method.Described water-oil separating nethike embrane is the hydrophilic polymer clad that is doped with inorganic nano-particle that is coated with micron thickness in 100～300 purpose screen of fabric, simultaneously be the spherical protuberances that is uniform-distribution with at many levels micro-meter scale at clad, on the micro-meter scale projection and be uniform-distribution with the spherical protuberances of nanoscale in the micron projection interval, the thickness of the clad of described micron thickness is 11～50 microns; The spherical protuberances particle diameter of described micro-meter scale is 1～50 micron; The particle diameter of the spherical protuberances of described nano-scale width is 10～900 nanometers; Described water-oil separating nethike embrane is 0 ° to the contact angle of water and oil in air, under water to the contact angle of oil droplet greater than 150 °.
Simple function UV of the present invention solidifies oligomer, difunctionality UV solidifies oligomer and sense UV curing oligomer is hydrophily or water-soluble oligomer; Wherein the single functionality oligomer mainly forms the hydrophilic polymer molecule brush on the surface of film; The bifunctionality oligomer is main film forming substance; The polyfunctionality oligomer is crosslinking agent, is conducive to form network structure.
The invention provides the application of described super water-oil separating nethike embrane hydrophilic and super oleophobic under water in the processing of the separation of oil water mixture and oil-polluted water.
As can be used for containing rapeseed oil, linseed oil, soybean oil, peanut oil, corn oil, cottonseed oil, olive oil, sesame oil, rice bran oil, camellia oil, sunflower seeds wet goods edible oil; The long chain alkanes such as dodecane, tridecane, the tetradecane, pentadecane, hexadecane; Benzene,toluene,xylene, trimethylbenzene, ethylbenzene, propyl benzene, styrene and other aromatic hydrocarbon; The organic matters such as methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, vinylacetate, ethyl acetate, butyl acetate, carbon tetrachloride, carrene, diiodomethane; The water-oil separating of crude oil, gasoline, kerosene, diesel oil, all kinds of solvent naphtha, lubricated wet goods.
Inorganic nano-particle rich surface hydroxyl of the present invention, and do not contain other organic groups, particle diameter is 10～500nm.The aperture of the mesh of micro-meter scale is 30～170 microns; The aperture of the mesh of micro-meter scale is 10～100 microns; The thickness of the clad of micron thickness is 11～50 microns; The height of the projection of nano-scale width is 10～900 nanometers.
With respect to prior art, the present invention has following advantage:
1) the simple function oligomer in the photocuring oligomer of the present invention has formed the polymer molecule brush on the surface of film behind film-forming, thereby so that the hydrophilic effect of film is better, simultaneously under water, the hydrophilic polymer molecule brushing tool has fabulous anti-oily adhesiving effect.
2) the prepared water-oil separating film of the present invention carries out water-oil separating and relies on gravity and capillary force fully, thereby have with low cost, energy consumption is lower, good separating effect, speed are fast, need not other chemical addition agents, have no side effect and secondary pollution, the anti-oil droplet of automatically cleaning pollutes, and nethike embrane easily reclaims repeatedly recycling, can be used for preparing on a large scale.
Water flux was large, simple to operate when 3) the prepared water-oil separating film of the present invention was processed, and except the material Transfer energy consumption, without additional energy source consumption, the film surface has self-cleaning function, was easy to clean and recycling, and the decline of membrane flux is slow.
4) equal inexpensive being easy to get of the raw material that adopt of the preparation of water-oil separating nethike embrane of the present invention, and all do not have toxicity, environmental friendliness can not cause secondary pollution, can not produce injury to operator's health yet;
5) manufacture craft of the present invention and equipment are simple, are easy to realize, are applicable to large-scale production on a large scale.
Description of drawings
Fig. 1 is embodiment 1 rich surface hydroxyl nano silicon infrared spectrogram.
Fig. 2 is embodiment 1 cleaning blank stainless steel cloth surface water contact angle (91.3 °).
Fig. 3 is embodiment 1 micro-nano structure stainless steel cloth film coated surface water contact angle (0 °).
Fig. 4 is that 200 times of the blank stainless steel cloth of 300 orders amplify SEM figure.
Fig. 5 is that 200 times of embodiment 1 gained nethike embrane amplify SEM figure.
Fig. 6 is that 500 times of embodiment 1 gained nethike embrane amplify SEM figure.
Fig. 7 is that 5000 times of embodiment 1 gained nethike embrane amplify SEM figure.
The specific embodiment
Embodiment 1: water-based UV solidifies oligomer/nanometer SiO
2The preparation of stainless steel cloth water-oil separating nethike embrane
(1) with a 15 * 15mm
2300 purpose stainless steel cloths immerse respectively in order in distilled water, ethanol or acetone, the distilled water each at 150W, ultrasonic cleaning 8min hangs up at normal temperatures and dries under the 40KHz;
(2) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 ℃ of water bath with thermostatic control heating are also constantly stirred, after stirring, take by weighing the 0.5g mass concentration and be 25% ammoniacal liquor, add in the 30g deionized water, splash in the four-hole boiling flask with the speed of constant flow pump with 1ml/min, discharging prepares the approximately Nano silica sol of 10nm of particle diameter behind the insulation 4h, and the nano particle mass content is 20%.Adopt Fourier's infrared tester to test the structure of the nano particle that is synthesized, by accompanying drawing 1 infrared spectrogram as seen, at 3400cm
?1There is a strong absworption peak at the place, for Qiang Ji ?the absworption peak of OH, 930cm
?1The place for silanol base Si ?the stretching vibration peak of OH, 1000～1100cm
?1Locate strong and wide absworption peak for for Si ?the stretching vibration absworption peak of O, this place also exist simultaneously Si ?O ?the stretching vibration absworption peak of Si (Fourth Ring body).Illustrate tetraethoxysilane all hydrolytic condensation generated the nanometer SiO of rich surface hydroxyl
2
(3) 10 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3102), 60 parts of difunctionality UV curing oligomer (Changxing, Taiwan EM226); Ludox, 1 part of water-soluble photoinitiator Darocur2959 (Switzerland Ciba company), 5 parts of emulsifying agent detergent alkylate sulphur sodium sulfonates that 20 parts of multifunctional UV solidify oligomer (Changxing, Taiwan EM2386), 500 parts of steps (2) gained add in the 1000ml beakers and mix, at 500W, ultrasonic dispersion 10min is uniformly dispersed with assurance under the 40KHz;
(4) stainless steel cloth of step (1) being cleaned immerses 10min in the resulting mixed solution of step (3), to guarantee that silk screen is fully soaked into, then vertically lifting and hanging over temperature is to toast 30min in 80 ℃ the constant-temperature vacuum drying box, then nethike embrane is put into uv cure machine and is solidified 3min.
Adopt the contact angle of Dataphysics OCA40Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.Be that 200 times the visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph is the hydrophilic polymer clad that is doped with inorganic nano-particle that is coated with 50 micron thickness at 300 order stainless steel wires on the net by the surface of film in multiplication factor, as shown in Figure 5; Being as seen 1000 times ESEM picture exists 40 micron pore size in the silk screen interval micropore in multiplication factor, all is the thick just projection of structure of micro-nano around the micropore, as shown in Figure 6 simultaneously; Further amplify, multiplication factor be 10000 times the ESEM picture as seen, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 1 micron, simultaneously on the micron ball and exist the nanosphere that particle diameter is 100nm between the micron ball interval, as shown in Figure 7.
(5) in air, adopt the silk screen that obtains in surface tension tester (OCA) measuring process (1) empty silk screen and the step (5) that the contact angle of 3 microliters of water is respectively 91.7 ° and 0 °, see accompanying drawing 2 and 3, prove that this nethike embrane has super hydrophilicity.
(6) silk screen that obtains in the step (4) is fixed in the general water-oil separating membrane module, water is dyed redness with red ink, with No. 100 solvent naphthas 1:1 mixing and stirring by volume, oil-water mixture is poured in this water-oil separating membrane module, hydrophilic polymer water absorption and swelling, red source, water source be infiltration downwards constantly, and No. 100 solvent naphthas are blocked on the film all the time, even redness does not all have residually on the telolemma, has reached oil-water separation.
Embodiment 2: water-based UV solidifies oligomer/nanometer SiO
2The preparation of copper mesh water-oil separating nethike embrane
(1) with a 15 * 15mm
2100 purpose copper mesh immerse respectively in order in distilled water, ethanol, the distilled water each at 100W, clean 10min under the 20KHz, hang up at normal temperatures and dry;
(2) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 80 ℃ of water bath with thermostatic control heating are also constantly stirred, after stirring, take by weighing the 0.5g mass concentration and be 25% hydrochloric acid, add in the 30g deionized water, splash in the four-hole boiling flask with the speed of constant flow pump with 1ml/min, discharging prepares the Nano silica sol of particle diameter 500nm behind the insulation 4h, and the nano particle mass content is 35%.Adopt Fourier's infrared tester to test the structure of the nano particle that is synthesized, resulting structures figure is similar to Fig. 1.
(3) 50 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3103), 60 parts of difunctionality UV curing oligomer (Changxing, Taiwan EM227); Ludox, 5 parts of water-soluble photoinitiator Esacure KIP150 (Lamberti company), 5 parts of emulsifying agent detergent alkylate sulphur sodium sulfonates that 10 parts of multifunctional UV solidify oligomer (Changxing, Taiwan EM2386), 300 parts of steps (2) gained add in the 500ml beakers and mix, at 300W, ultrasonic dispersion 10min is uniformly dispersed with assurance under the 20KHz;
(4) adopt high-pressure spray gun under the pressure of 0.6Mpa, the resulting mixed solution of step (3) to be sprayed at the copper mesh surface that step (1) is cleaned, to guarantee the coating of 10 microns of silk screen surface uniform distribution one decks, hang over temperature and be in 120 ℃ the constant-temperature vacuum drying box and toast 30min, then nethike embrane is put into uv cure machine and solidified 5min.
Adopt the contact angle of Dataphysics OCA40Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.Be that 200 times the visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph is the hydrophilic polymer clad that is doped with inorganic nano-particle that is coated with 50 micron thickness at 300 order copper mesh by the surface of film in multiplication factor, to shown in Figure 5 similar; Being as seen 1000 times ESEM picture exists 40 micron pore size in the silk screen interval micropore in multiplication factor, all is the thick just projection of structure of micro-nano around the micropore, to shown in Figure 6 similar simultaneously; Further amplify, multiplication factor be 10000 times the ESEM picture as seen, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on the micron ball and exist the nanosphere that particle diameter is 100nm between the micron ball interval, to shown in Figure 7 similar.
(5) in air, adopt the silk screen that obtains in surface tension tester (OCA) measuring process (1) empty silk screen and the step (5) to the contact angle of 3 microliters of water, similar with 3 to accompanying drawing 2 respectively, prove that this nethike embrane has super hydrophilicity.
(6) silk screen that obtains in the step (4) is fixed in the general water-oil separating membrane module, water is dyed redness with red ink, with diesel oil 1:1 mixing and stirring by volume, oil-water mixture is poured in this water-oil separating membrane module, hydrophilic polymer water absorption and swelling, red source, water source be infiltration downwards constantly, and diesel oil is blocked on the film all the time, even on the telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 3: water-based UV solidifies oligomer/nanometer SiO
2The preparation of aluminium wire netting water-oil separating nethike embrane
(1) with a 15 * 15mm
2200 purpose aluminium wire nettings immerse respectively in order in distilled water, ethanol or acetone, the distilled water each at 150W, ultrasonic cleaning 10min hangs up at normal temperatures and dries under the 40KHz;
(2) in four-hole boiling flask, add 50g tetramethoxy-silicane, 100g absolute ethyl alcohol and 20g deionized water, 35 ℃ of water bath with thermostatic control heating are also constantly stirred, after stirring, take by weighing the 0.5g mass concentration and be 25% sodium acid carbonate, add in the 30g deionized water, splash in the four-hole boiling flask with the speed of constant flow pump with 1.5ml/min, discharging prepares the Nano silica sol of particle diameter 200nm behind the insulation 5h, and the nano particle mass content is 35%.Adopt Fourier's infrared tester to test the structure of the nano particle that is synthesized, resulting structures figure is similar to Fig. 1;
(3) 20 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3103), 80 parts of difunctionality UV curing oligomer (Changxing, Taiwan EM326); Ludox, 5 parts of water-soluble photoinitiator Irgacure891DW (Ciba special chemical article company), 1 part of emulsifying agent detergent alkylate sulphur sodium sulfonate that 20 parts of multifunctional UV solidify oligomer (Changxing, Taiwan EM2386), 300 parts of steps (2) gained add in the 500ml beaker and mix, at 500W, ultrasonic dispersion 10min is uniformly dispersed with assurance under the 40KHz;
(4) aluminium wire netting of step (1) being cleaned immerses 10min in the resulting mixed solution of step (3), to guarantee that silk screen is fully soaked into, then vertically lifting and hanging over temperature is to toast 30min in 80 ℃ the constant-temperature vacuum drying box, then nethike embrane is put into uv cure machine and is solidified 3min.
Adopt the contact angle of Dataphysics OCA40Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.Be that 200 times the visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph is the hydrophilic polymer clad that is doped with inorganic nano-particle that is coated with 50 micron thickness at 300 order copper mesh by the surface of film in multiplication factor, to shown in Figure 5 similar; Being as seen 1000 times ESEM picture exists 40 micron pore size in the silk screen interval micropore in multiplication factor, all is the thick just projection of structure of micro-nano around the micropore, to shown in Figure 6 similar simultaneously; Further amplify, multiplication factor be 10000 times the ESEM picture as seen, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on the micron ball and exist the nanosphere that particle diameter is 100nm between the micron ball interval, to shown in Figure 7 similar.
(5) in air, adopt the silk screen that obtains in surface tension tester (OCA) measuring process (1) empty silk screen and the step (6) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water, prove that this nethike embrane has super hydrophilicity.
(6) silk screen that obtains in the step (4) is fixed in the general water-oil separating membrane module, water is dyed redness with red ink, with dodecane 1:1 mixing and stirring by volume, oil-water mixture is poured in this water-oil separating membrane module, hydrophilic polymer water absorption and swelling, red source, water source be infiltration downwards constantly, and dodecane is blocked on the film all the time, even on the telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 4: water-based UV solidifies oligomer/nanometer SiO
2The preparation of nylon mesh water-oil separating nethike embrane
(1) with a 15 * 15mm
2300 purpose nylon mesh immerse respectively in order in distilled water, ethanol or acetone, the distilled water each at 100W, ultrasonic cleaning 10min hangs up at normal temperatures and dries under the 20KHz;
(2) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 ℃ of water bath with thermostatic control heating are also constantly stirred, after stirring, take by weighing the 0.5g mass concentration and be 25% sulfuric acid, add in the 30g deionized water, splash in the four-hole boiling flask with the speed of constant flow pump with 1.5ml/min, discharging prepares the approximately Nano silica sol about 20nm of particle diameter behind the insulation 4h, and the nano particle mass content is 35%.Adopt Fourier's infrared tester to test the structure of the nano particle that is synthesized, resulting structures figure is similar to Fig. 1;
(3) 20 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3102), 80 parts of difunctionality UV curing oligomer (Changxing, Taiwan EM327); 20 parts of multifunctional UV solidify the Ludox of oligomer (the special IRR210 of company of cyanogen), 200 parts of steps (2) gained, 5 parts of water-soluble photoinitiator WB ?4784 (Britain Ward ?Blenkinsop company), 1 part of emulsifying agent detergent alkylate sulphur sodium sulfonate add in the 500ml beaker and mix, at 300W, ultrasonic dispersion 10min is uniformly dispersed with assurance under the 20KHz;
(4) nylon mesh of step (1) being cleaned immerses 10min in the resulting mixed solution of step (3), to guarantee that silk screen is fully soaked into, then vertically lifting and hanging over temperature is to toast 30min in 80 ℃ the constant-temperature vacuum drying box, then nethike embrane is put into uv cure machine and is solidified 5min.
Adopt the contact angle of Dataphysics OCA40Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.Be that 200 times the visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph is the hydrophilic polymer clad that is doped with inorganic nano-particle that is coated with 50 micron thickness at 300 order copper mesh by the surface of film in multiplication factor, to shown in Figure 5 similar; Being as seen 1000 times ESEM picture exists 40 micron pore size in the silk screen interval micropore in multiplication factor, all is the thick just projection of structure of micro-nano around the micropore, to shown in Figure 6 similar simultaneously; Further amplify, multiplication factor be 10000 times the ESEM picture as seen, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on the micron ball and exist the nanosphere that particle diameter is 100nm between the micron ball interval, to shown in Figure 7 similar.
(5) in air, adopt the silk screen that obtains in surface tension tester (OCA) measuring process (1) empty silk screen and the step (6) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water, prove that this nethike embrane has super hydrophilicity.
(6) silk screen that obtains in the step (4) is fixed in the general water-oil separating membrane module, water is dyed redness with red ink, with rapeseed oil 1:1 mixing and stirring by volume, oil-water mixture is poured in this water-oil separating membrane module, hydrophilic polymer water absorption and swelling, red source, water source be infiltration downwards constantly, and rapeseed oil is blocked on the film all the time, on the telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 5: water-based UV solidifies oligomer/nanometer SiO
2The preparation of polyvinyl silk screen water-oil separating nethike embrane
(1) with a 15 * 15mm
2300 purpose polyvinyl silk screens immerse respectively in order in distilled water, ethanol or acetone, the distilled water each at 100W, ultrasonic cleaning 5min hangs up at normal temperatures and dries under the 20KHz;
(2) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 ℃ of water bath with thermostatic control heating are also constantly stirred, after stirring, take by weighing the 0.5g mass concentration and be 25% nitric acid, add in the 30g deionized water, splash in the four-hole boiling flask with the speed of constant flow pump with 1.5ml/min, discharging prepares the approximately Nano silica sol about 50nm of particle diameter behind the insulation 4h, and the nano particle mass content is 35%.Adopt Fourier's infrared tester to test the structure of the nano particle that is synthesized, resulting structures figure is similar to Fig. 1;
(3) 10 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3101), 80 parts of difunctionality UV curing oligomer (the special EB2002 of company of cyanogen); 20 parts of multifunctional UV solidify the Ludox of oligomer (PE55WN of BASF AG), 400 parts of steps (2) gained, 5 parts of water-soluble photoinitiator WB ?4785 (Britain Ward ?Blenkinsop company), 1 part of emulsifying agent detergent alkylate sulphur sodium sulfonate add in the 500ml beaker and mix, under the disk dispersion machine, disperse 15min to be uniformly dispersed guaranteeing with rotating speed 1000r/min;
(4) the polyvinyl silk screen of step (1) being cleaned immerses 10min in the resulting mixed solution of step (3), to guarantee that silk screen is fully soaked into, then vertically lifting and hanging over temperature is to toast 30min in 80 ℃ the constant-temperature vacuum drying box, then nethike embrane is put into uv cure machine and is solidified 5min.
Adopt the contact angle of Dataphysics OCA40Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.Be that 200 times the visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph is the hydrophilic polymer clad that is doped with inorganic nano-particle that is coated with 50 micron thickness at 300 order copper mesh by the surface of film in multiplication factor, to shown in Figure 5 similar; Being as seen 1000 times ESEM picture exists 40 micron pore size in the silk screen interval micropore in multiplication factor, all is the thick just projection of structure of micro-nano around the micropore, to shown in Figure 6 similar simultaneously; Further amplify, multiplication factor be 10000 times the ESEM picture as seen, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on the micron ball and exist the nanosphere that particle diameter is 100nm between the micron ball interval, to shown in Figure 7 similar.
(5) in air, adopt the silk screen that obtains in surface tension tester (OCA) measuring process (1) empty silk screen and the step (5) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water, prove that this nethike embrane has super hydrophilicity.
(6) silk screen that obtains in the step (4) is fixed in the general water-oil separating membrane module, water is dyed redness with red ink, with trimethylbenzene 1:1 mixing and stirring by volume, oil-water mixture is poured in this water-oil separating membrane module, hydrophilic polymer water absorption and swelling, red source, water source be infiltration downwards constantly, and trimethylbenzene is blocked on the film all the time, on the telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 6: water-based UV solidifies oligomer/nano-TiO
2The preparation of aramid fiber silk screen oil-water separating net film
(1) with a 15 * 15mm
2300 purpose aramid fiber silk screens immerse respectively in order in distilled water, ethanol or acetone, the distilled water each at 100W, ultrasonic cleaning 10min hangs up at normal temperatures and dries under the 20KHz;
(2) in four-hole boiling flask, add 50g purity titanium tetraethoxide, 100g absolute ethyl alcohol and 20g deionized water, 35 ℃ of water bath with thermostatic control heating are also constantly stirred, after stirring, taking by weighing the 0.5g mass concentration and be 25% NaOH adds in the 30g deionized water, splash in the four-hole boiling flask with the speed of constant flow pump with 1.5ml/min, discharging prepares the approximately nano-titanium colloidal sol about 50nm of particle diameter behind the insulation 4h, and the nano particle mass content is 35%.Adopt Fourier's infrared tester to test the structure of the nano particle that is synthesized, resulting structures figure is similar to Fig. 1;
(3) 20 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3102), 80 parts of difunctionality UV curing oligomer (the special EB11 of company of cyanogen); Mix in the Ludox of 20 parts of multifunctional UV curing oligomer (lid Si Tafu company 2000), 400 parts of steps (2) gained, 5 parts of water-soluble photoinitiator WB ?4789 (Britain Ward ?Blenkinsop company), 1 part of emulsifying agent detergent alkylate sulphur sodium sulfonate adding 500ml beaker, under the disk dispersion machine, disperse 10min to be uniformly dispersed with assurance with rotating speed 1500r/min;
(4) the aramid fiber silk screen of step (1) being cleaned immerses 10min in the resulting mixed solution of step (3), to guarantee that silk screen is fully soaked into, then vertically lifting and hanging over temperature is to toast 30min in 80 ℃ the constant-temperature vacuum drying box, then nethike embrane is put into uv cure machine and is solidified 5min.
Adopt the contact angle of Dataphysics OCA40Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.Be that 200 times the visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph is the hydrophilic polymer clad that is doped with inorganic nano-particle that is coated with 50 micron thickness at 300 order copper mesh by the surface of film in multiplication factor, to shown in Figure 5 similar; Being as seen 1000 times ESEM picture exists 40 micron pore size in the silk screen interval micropore in multiplication factor, all is the thick just projection of structure of micro-nano around the micropore, to shown in Figure 6 similar simultaneously; Further amplify, multiplication factor be 10000 times the ESEM picture as seen, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on the micron ball and exist the nanosphere that particle diameter is 100nm between the micron ball interval, to shown in Figure 7 similar.
(5) in air, adopt the silk screen that obtains in surface tension tester (OCA) measuring process (1) empty silk screen and the step (5) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water, prove that this nethike embrane has super hydrophilicity.
(6) silk screen that obtains in the step (4) is fixed in the general water-oil separating membrane module, water is dyed redness with red ink, with methyl methacrylate 1:1 mixing and stirring by volume, oil-water mixture is poured in this water-oil separating membrane module, hydrophilic polymer water absorption and swelling, red source, water source be infiltration downwards constantly, and methyl methacrylate is blocked on the film all the time, even on the telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 7: water-based UV solidifies oligomer/nano-TiO
2The preparation of terylene silk net water-oil separating nethike embrane
(1) with a 15 * 15mm
2300 purpose terylene silk nets immerse respectively in order in distilled water, ethanol or acetone, the distilled water each at 150W, ultrasonic cleaning 10min hangs up at normal temperatures and dries under the 40KHz;
(2) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 ℃ of water bath with thermostatic control heating are also constantly stirred, after stirring, take by weighing the 0.5g mass concentration and be 25% boric acid, add in the 30g deionized water, splash in the four-hole boiling flask with the speed of constant flow pump with 1.5ml/min, discharging prepares the approximately nano-titanium colloidal sol about 50nm of particle diameter behind the insulation 4h, and the nano particle mass content is 35%.Adopt Fourier's infrared tester to test the structure of the nano particle that is synthesized, resulting structures figure is similar to Fig. 1;
(3) 20 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3102), 80 parts of difunctionality UV curing oligomer (Changxing EM327); 20 parts of multifunctional UV solidify the Ludox of oligomer (the modest UV of moral ?14), 400 parts of steps (2) gained, 5 parts of water-soluble photoinitiator WB ?4792 (Britain Ward ?Blenkinsop company), 1 part of emulsifying agent detergent alkylate sulphur sodium sulfonate add in the 500ml beaker and mix, at 300W, ultrasonic dispersion 10min is uniformly dispersed with assurance under the 20KHz;
(4) terylene silk net of step (1) being cleaned immerses 10min in the resulting mixed solution of step (3), to guarantee that silk screen is fully soaked into, then vertically lifting and hanging over temperature is to toast 30min in 80 ℃ the constant-temperature vacuum drying box, then nethike embrane is put into uv cure machine and is solidified 5min.
Adopt the contact angle of Dataphysics OCA40Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.Be that 200 times the visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph is the hydrophilic polymer clad that is doped with inorganic nano-particle that is coated with 50 micron thickness at 300 order copper mesh by the surface of film in multiplication factor, to shown in Figure 5 similar; Being as seen 1000 times ESEM picture exists 40 micron pore size in the silk screen interval micropore in multiplication factor, all is the thick just projection of structure of micro-nano around the micropore, to shown in Figure 6 similar simultaneously; Further amplify, multiplication factor be 10000 times the ESEM picture as seen, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on the micron ball and exist the nanosphere that particle diameter is 100nm between the micron ball interval, to shown in Figure 7 similar.
(5) in air, adopt the silk screen that obtains in surface tension tester (OCA) measuring process (1) empty silk screen and the step (5) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water, prove that this nethike embrane has super hydrophilicity.
(6) silk screen that obtains in the step (4) is fixed in the general water-oil separating membrane module, water is dyed redness with red ink, with hexadecane 4:1 mixing and stirring by volume, add the 0.2g neopelex, magnetic agitation 15min makes the O/W emulsion, emulsion is poured in this water-oil separating membrane module, the hydrophilic polymer water absorption and swelling, red source, water source is infiltration downwards constantly, and hexadecane is blocked on the film all the time, even on the telolemma redness all do not have residual, thereby reached oil-water separation.
Claims (10)
1.UV solidify the super hydrophilic preparation method of super oleophobic water-oil separating film under water that reaches, it is characterized in that comprising the steps:
(1) with 100～300 purpose screen of fabric ultrasonic cleaning, normal temperature dries;
(2) Cai with Rong Jiao ?gel method, take tetraethoxysilane, tetramethoxy-silicane or purity titanium tetraethoxide as raw material, with alcohols and water in mass ratio 1:5～5:1 be mixed with cosolvent, with raw material and cosolvent in mass ratio 1:1～1:5 be mixed in 20～80 ℃ of waters bath with thermostatic control, stirring, behind 5～10min, drip catalyst, insulation 4～5h namely obtains Nano sol; Described alcohols is one or more in ethanol, propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol and the isobutanol; Described catalyst is hydrochloric acid, nitric acid, boric acid, sulfuric acid, ammoniacal liquor, sodium acid carbonate or NaOH;
(3) 10～50 parts of simple function UV are solidified oligomer, 60～80 parts of difunctionality UV curing oligomer; 10～20 parts of multifunctional UV solidify oligomer, the Nano sol of 200～500 parts of steps (2) gained, 1～5 part of light trigger and 1～5 part of emulsifying agent and mix, and disperse 10～20min with ultrasonic dispersion or disk dispersion machine under 1000～2000r/min; Get the UV solidified aqueous coating; It is methoxy polyethylene glycol acrylate or methoxy polyethylene glycol methacrylate-styrene polymer that described simple function UV solidifies oligomer; It is polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, water soluble acrylic acid ester oligomer, aqueous polyurethane acrylate oligomer, waterborne polyester acrylate oligomer or waterborne epoxy acrylate oligomer that described difunctionality UV solidifies oligomer; It is ethoxyquin trimethylolpropane triacrylate, water soluble acrylic acid ester oligomer, aqueous polyurethane acrylate oligomer, waterborne polyester acrylate oligomer or waterborne epoxy acrylate oligomer that described multifunctional UV solidifies oligomer; Described light trigger be water-soluble photoinitiator Darocur2959, Esacure KIP150, Irgacure891DW, QTX, BTC, BPQ, WB ?4784, WB ?4785, WB ?4789 or WB ?4792; Described emulsifying agent is neopelex;
(4) with in the UV solidified aqueous coating in the silk screen immersion step (3) that obtains in the step (1), behind immersion 5～20min it has vertically been lifted, perhaps adopted high-pressure spray gun directly the UV solidified aqueous coating to be sprayed on the silk screen; With soak or spraying after silk screen hang over and maintain the temperature at 80～120 ℃ of oven dry in the constant-temperature vacuum baking oven, then under uv cure machine, solidify 3～5min, get the super hydrophilic and water-oil separating nethike embrane of super oleophobic under water.
2. UV according to claim 1 solidifies the super hydrophilic preparation method of super oleophobic water-oil separating film under water that reaches, it is characterized in that: described screen of fabric is stainless steel cloth, copper mesh, aluminium wire netting, nylon mesh, polyvinyl silk screen, aramid fiber silk screen, terylene silk net or acrylic fibre fabric web.
3. UV according to claim 1 solidifies the super hydrophilic preparation method of super oleophobic water-oil separating film under water that reaches, and it is characterized in that: the supersonic frequency of described ultrasonic cleaning is 20～40KHz, and power bracket is 100～150W.
4. UV according to claim 1 solidifies the super hydrophilic preparation method of super oleophobic water-oil separating film under water that reaches, and it is characterized in that: the supersonic frequency of described ultrasonic dispersion is 20～40KHz, and power bracket is 300～500W.
5. UV according to claim 1 solidifies the super hydrophilic preparation method of super oleophobic water-oil separating film under water that reaches, it is characterized in that: described ultrasonic cleaning is for clean with ultrasonic washing with clean water first, then with absolute ethyl alcohol or acetone ultrasonic cleaning, use again the distilled water ultrasonic cleaning clean.
6. UV according to claim 1 solidifies the super hydrophilic preparation method of super oleophobic water-oil separating film under water that reaches, and it is characterized in that: the speed of described dropping catalysis is 1～10ml/min; The ultraviolet wavelength of described uv cure machine is 245～405nm.
7. UV according to claim 1 solidifies the super hydrophilic preparation method of super oleophobic water-oil separating film under water that reaches, and it is characterized in that: the nano particle diameter in the described Nano sol is controlled at 10～500nm, and the nano particle mass content is 20～35%.
8. UV claimed in claim 1 solidifies super hydrophilic and super oleophobic water-oil separating film under water, it is characterized in that, its by claim 1 ?7 each described preparation methods make.
9. UV according to claim 8 solidifies the super hydrophilic super oleophobic water-oil separating film under water that reaches, it is characterized in that, described water-oil separating nethike embrane is the hydrophilic polymer clad that is doped with inorganic nano-particle that is coated with micron thickness in 100～300 purpose screen of fabric, simultaneously be the spherical protuberances that is uniform-distribution with at many levels micro-meter scale at clad, on the micro-meter scale projection and be uniform-distribution with the spherical protuberances of nanoscale in the micron projection interval, the thickness of the clad of described micron thickness is 11～50 microns; The spherical protuberances particle diameter of described micro-meter scale is 1～50 micron; The particle diameter of the spherical protuberances of described nano-scale width is 10～900 nanometers; Described water-oil separating nethike embrane is 0 ° to the contact angle of water and oil in air, under water to the contact angle of oil droplet greater than 150 °.
10. claim 8 or 9 described UV solidify the super hydrophilic and application of super oleophobic water-oil separating film in the processing of the separation of oil water mixture and oil-polluted water under water.
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